Photochemistry of 5-Membered Heteroaryl(Trifluoromethyl)Carbenes In

University of Nevada, Reno

“Photochemistry of 5-Membered Heteroaryl(trifluoromethyl)carbenes in

Low Temperature Matrices”

A dissertation submitted in partial fulfillment of the

requirements for the degree of Doctor of Philosophy in

Chemistry

Rajendra Ghimire

Dr. Robert S. Sheridan/Dissertation Advisor

December, 2012

THE GRADUATE SCHOOL

We recommend that the dissertation prepared under our supervision by

RAJENDRA GHIMIRE

entitled

Photochemistry of 5-Membered Heteroaryl(trifluoromethyl)carbenes in Low Temperature Matrices

be accepted in partial fulfillment of the requirements for the degree of

DOCTOR OF PHILOSOPHY

Robert S. Sheridan, Ph.D., Advisor

Vincent J. Catalano, Ph.D., Committee Member

Benjamin T. King, Ph.D., Committee Member

Jonathan Weinstein, Ph.D., Committee Member

James H. Trexler, Ph.D., Graduate School Representative

Marsha H. Read, Ph. D., Dean, Graduate School

December, 2012

Abstract

We have explored the photochemical reactions of 3-benzothienyl(trifluoromethyl)-,

3-N-methyl-indolyl(trifluoromethyl)-, 2-N-methyl-indolyl(trifluoromethyl)-, benzo-

thiazolyl(trifluoromethyl)-, and benzoxazolyl(trifluoromethyl)carbenes in low

temperature N 2 matrices. The 3-benzothienyl(trifluoromethyl)carbene rearranged to

several new reactive intermediates such as bicyclic intermediate, ring expanded

carbene and spiro product, which were not observed or characterized before. The 3- benzothienyl(trifluoromethyl)diazirine led us to a new realm of UV-vis transparent

diazirines, which behave as normal diazirine photochemically, but have very weak

nπ∗ absorptions which are not visible in experimental UV-vis spectra. Also, we were

able to synthesize diazirine precursors of both 2- and 3- N-methyl- indolylcarbene

and observed and characterized their carbenes spectroscopically. All three carbenes

mentioned above are ground state singlets. In the case of the benzothiazole and benzoxazole system, we were able to observe and characterize both syn and anti

conformers of diazirine in low temperature matrices. The CF 3 carbenes behaved similarly to chloro carbenes photochemically in both benzothiazole and benzoxazole, but the CF 3 carbenes were triplet ground state compared to the singlet chloro carbenes. ii

We believe our work will add to understanding of the reactivity and electronic states of 5-membered heteroaryl carbenes. Application wise, synthesis of heteroaryl CF 3

diazirines might add to the possibility of new photoaffinity labeling agents.

Acknowledgements

My sincere and deepest gratitude goes to my advisor, Professor Robert S. Sheridan,

for his extraordinary patience and exceptional mentoring throughout my graduate

career, in both academic and personal areas. His unconditional support and guidance

have helped me to better prepare for upcoming challenges, in both personal and professional career, and I hope it continues.

I want to thank previous and current Sheridan group members, Dr. Peter Zuev, Dr.

Andrea Song, Dr. Jian Wang, Chengliang Zhu, Pei Wang, Binya Yang, Emilia Groso,

Danielle Poteete, Rachel Lecker and Sean Ross for their friendship, support and

guidance.

I want to thank my committee members for their time, patience and continuous

guidance. Finally, I want to thank my friends and family. My heartfelt thanks goes to

my parents, my brother and especially for my wife, Shikha, who has been with me,

with love, support and patience, at all times.

iii

Table of Contents

Abstract i

Acknowledgements ii

Table of Contents iii

List of Schemes vii

List of Figures xii

Introduction 1

1. Background

1.1. Methylene 2

1.2. Stability and Substitution Effect 5

1.3. Philicity of Carbenes 7

1.4. Observation and Characterization 9

1.5. Applications 11

1.5.1. Photoaffinity labeling 12

1.6. Reactivity of Carbenes 13

1.6.1. Addition 14

1.6.2. Rearrangement 15

1.7. Phenylcarbene 15

1.7.1. Investigation of C 6H7 potential energy surface 21

1.7.2. Phenylchlorocarbene 22 iv

1.7.3. Tolylcarbenes 23

1.8. Naphthylcarbenes 26

1.8.1. Naphthylchlorocarbenes 34

1.9. Vinylcarbenes 36

1.10. Heteroarylcarbenes 38

1.10.1. Pyridylcarbenes 38

1.10.2. Investigation of C 6H7N potential energy surface 44

1.10.3. Naphthylnitrenes 45

1.10.4. 5-membered heteroarylcarbenes 46

1.11. Cyclic Cumulenes 60

1.11.1. 1,2-cyclohexadiene 61

1.11.2. Cumulene From Heteroarylcarbenes 63

1.11.2.1. Atomic Carbon Reaction 63

1.11.2.2. Theoretical study of 6-membered allene 65

1.11.3. Direct observation and characterization of cyclic cumulene 68

1.11.3.1. Observation and characterization of didehydropyran 68

1.11.3.2. Observation and characterization of didehydrothiopyran 70

1.11.3.3. Comparative study of oxo cumulene vs thio cumulene 71

1.11.4. Direct observation and characterization of Didehydrobenzoxazine 74

1.11.4.1. B3LYP energies of benzofuran and benzoxazole system 75

1.11.5. Observation and characterization of didehydrobenzothiazine 75

1.11.6. Observation and characterization of CF 3 didehydrobenzothiopyran 78 v

1.11.7. CF 3 vs Cl cumulene 79

1.12. Application of heteroarylcarbenes 80

2.Research Objective 83

2.1. Trifluoromethyl diazirines 85

2.2. 3-Heteroarylcarbenes 85

3.Result and Discussion 87

3.1. 3-benzothienyl(CF 3)carbene 87

3.1.1. Synthesis 88

3.1.2. Twisted diazirines 91

3.1.3. Observation and characterization of 3-benzothienyl(CF 3)carbene 96

3.1.4. Trapping reactions of 3-benzothienyl(CF 3)carbene 103

3.1.5. Photochemical rearrangement of 3-benzothienyl(CF 3)carbene 106

3.1.6. Deuterium labeling 115

3.1.7. Possible Mechanisms 119

3.1.8. Study of C 10 H5F3S Potential Energy Surface 120

3.2. N-Methyl-2-indolyl(CF 3)diazirine 122

3.2.1. Synthesis of N-Methyl-2-indolyl(CF 3)diazirine 124

3.2.2. Direct observation of N-Methyl-2-indolyl(CF 3)carbene 128

3.2.3. Photochemical rearrangement of N-Methyl-2-indolyl(CF 3)carbene 133

3.2.4. Study of C 11H8F3N Potential Energy Surface 138

3.3. N-Methyl-3-indolyl(CF 3)carbene 143

3.3.1. Synthesis of N-Methyl-3-indolyl(CF 3)diazirine 143 vi

3.3.2. Direct observation of N-Methyl-3-indolyl(CF 3)carbene 147

3.3.3. Trapping reactions of N-Methyl-3-indolyl(CF 3)carbene 150

3.3.4. Photochemical rearrangement of N-Methyl-3-indolyl(CF 3)carbene 151

3.3.5. Study of C 11H8F3N Potential Energy Surface 155

3.4. Benzothiazolyl(CF 3)carbene 158

3.4.1. Matrix isolation study of benzothiazolylchlorodiazirine 159

3.4.2. Synthesis of benzothiazolyl(CF 3)diazirine 163

3.4.3. Observation and characterization of syn and anti diazirine 166

3.4.4. Photochemical rearrangement of benzothiazolyl(CF 3)carbene 172

3.4.5. Trapping reactions of benzothiazolyl(CF 3)carbene 179

3.4.6. Study of C9H4N3F3S potential energy surface 181

3.5. Benzoxazolyl(CF 3)carbene 183

3.5.1. Synthesis of benzoxazolyl(CF 3)diazirine 183

3.5.2. Observation and characterization of syn and anti diazirine 186

3.5.3. Observation and characterization of benzoxazolyl(CF 3)carbene 189

3.5.4. Photochemical rearrangement of benzoxazolyl(CF 3)carbene 193

3.5.5. Trapping reaction of benzoxazolyl(CF 3)carbene 198

3.5.6. Study of C9H4N3F3O potential energy surface 199

3.6. Conclusion 201

3.7. Experimental 203

3.7.1. General 203

3.7.2. Matrix Isolation 203 vii

3.7.3. DFT Calculation 205

3.7.4. Synthesis 206

References 227

Supporting Information (B3LYP 6-31G**) 231

B3LYP 6-31+ G** Computed vibrational frequencies and intensities 359

NMR Spectra 389

List of Scheme

Scheme 1 .Thermolysis of phenyl diazomethane 1 to heptafulvalene 2 16

Scheme 2 .Thermolysis of phenyl diazomethane 1 16

Scheme 3 .Bicyclic product 6 proposed as an intermediate to 4 and 5 17

Scheme 4 .Matrix isolation study of phenyl diazomethane 1 diazirine 8 18

Scheme 5 .Matrix isolation study summary of phenyl carbene 3 20

Scheme 6.Thermal dimerization of 5 to 2 via 17 21

Scheme 7 .Phenylchlorocarbene 18 rearrangement to allene 19 22

Scheme 8 .Trapping reaction of phenylchlorocarbene 18 with O 2 23 viii

Scheme 9 .Thermolysis of tolyldiazomethanes 26 , 27 and 28 24

Scheme 10 .Tolylcarbene rearrangement 25

Scheme 11 .Flash vacuum pyrolysis of naphthyldiazomethane 41 and 42 27

Scheme 12 .Interconversion of napthylcarbene 39 and 44 28

Scheme 13 .Matrix isolation study of naphthyl diazomethane 41 and 42 29

Scheme 14 .Interconversion of 2-naphthylcarbene 44 into bicyclic intermediate 48 30

Scheme 15 .Interconversion of 1-naphthylcarbene 39 into bicyclic product 46 31

Scheme 16 .Spectroscopic evidence of benzocycloheptatetraene 45 32

Scheme 17 .Matrix isolation study of benzodiazocycloheptatriene 53 33

Scheme 18 .Matrix isolation study of benzocycloheptadienyldiazomethane 54 34

Scheme 19 .Matrix isolation study of1-naphthylchlorodiazirine 56 35

Scheme 20 .Matrix isolation study of 2-naphthylchlorodiazirine 59 35

Scheme 21 .Matrix isolation study of singlet vinylchlorocarbene 65 37

Scheme 22 .Matrix isolation study of cyclopentylchlorodiazirine 68 38

Scheme 23 .Interconversion of pyridylcarbene 75 and phenylnitrene 76 39

Scheme 24 .Matrix isolation study of pyridylcarbene interconversion 40 ix

Scheme 25 .Rearrangment of pyridylcarbene and phenylnitrene 41

Scheme 26 .Cyclic ylide 86 a possible link between carbenes 85 and 75 42

Scheme 27 .Wentrup matrix isolation study of pyridyl carbenes rearrangement 43

Scheme 28 .Matrix isolation study of deuterated 3-pyridylcarbene 93 44

Scheme 29 .Matrix isolation study of naphthylazides 97 and 98 46

Scheme 30 .Pyrolysis and trapping reaction of furyldiazomethane 108 47

Scheme 31 .Carbon addition reaction with furan 48

Scheme 32 .Matrix isolation study of furyldiazomethane 108 48

Scheme 33 .First observation and characterization of furylchlorocarbene 115 49

Scheme 34 .Thermolysis and trapping reactions of the thienyldiazomethane 120 50

Scheme 35 .Matrix isolation study of thienyldiazomethane 120 52

Scheme 36 .Spectroscopic characterization of thienylchlorocarbene 130 54

Scheme 37 .Thermolysis of 3-furyl and 3-thienyldiazomethane 137 and 138 55

Scheme 38 .Matrix isolation of 3-furyl and 3-thienyldiazomethane 137 and 138 56

Scheme 39 .Spectroscopic characterization of 3-furylchlorocarbene 152 57

Scheme 40 .Spectroscopic observation and characterization of 3-thienylcarbene 14 58 x

Scheme 41 .Spectroscopic characterization of 3-benzofurylchlorocarbene 158 59

Scheme 42 .Wentrup matrix isolation study to characterize 164 62

Scheme 43 .Sander matrix isolation study to characterize 164 63

Scheme 44 .Atomic carbon reaction with pyrrole 166 64

Scheme 45 .Atomic carbon reaction with thiophene 171 65

Scheme 46 .Study of C 5H4S potential energy surface 66

Scheme 47 .Spectroscopic characterization of cumulene 188 69

Scheme 48 .Spectroscopic characterization of cumulene 194 70

Scheme 49 .Spectroscopic characterization of didehydrobenzoxazine 199 74

Scheme 50 .Matrix isolation study of ketenimine 204 77

Scheme 51 .Matrix isolation study of cumulene 208 79

Scheme 52 .Isodesmic study of cumulene 194 vs 208 79

Scheme 53. Retrocyclization of furylcarbene 210 82

Scheme 54.Formation of indolizine 214 from enylpyridine 212 82

Scheme 55. Ene-ene-eyne cyclization via carbene intermediate 84

Scheme 56 .Synthesis of diazirine 223 91 xi

Scheme 57 .Trapping reaction of carbene 224 in 10 K, N 2 matrix 106

Scheme 58 . Photochemical rearrangement of carbene 224 115

Scheme 59 .Rearrangement of carbene 224 into 232 , 233 , 234 and 235 120

Scheme 60 .Synthesis of N-methyl-2-indolyl(CF 3)diazirine 244 128

Scheme 61 .Matrix isolation study of the diazirine 244 138

Scheme 62 .Synthesis of 3-indolyl(CF 3)ketone 250 and oxime 251 144

Scheme 63 .Synthesis of 3-N-methyl-indolyl(CF 3)diazirine 259 147

Scheme 64 .Trapping reaction of carbene 260 151

Scheme 65 .Matrix isolation study of diazirine 259 155

Scheme 66 .Synthesis of diazirine 202 159

Scheme 67 .Matrix isolation study of diazirine 202 162

Scheme 68.Possible mechanism for the formation of product 270 163

Scheme 69 .Possible mechanism for the synthesis of ketone 273 164

Scheme 70 .Synthesis of diazirine 277 166

Scheme 71 .Matrix isolation study of diazirine 277 178

Scheme 72 .Trapping reaction of carbene 278 with O 2 and HCl 181 xii

Scheme 73 .Synthesis of diazirine 288 187

Scheme 74 .Matrix isolation study of benzoxazolyl(CF 3)diazirine 288 195

Scheme 75 .Trapping reaction of carbene 289 with O 2 199

List of Figure

Figure 1 .Singlet and triplet carbenes 1

Figure 2 .Relationship between carbene geometry and frontier orbital 3

Figure 3 .Methylene singlet and triplet energy levels 4

Figure 4 .Resonance stabilization of singlet methylenechlorocarbene 5

Figure 5 .A carbene p-orbital interactions 6

Figure 6.N-heterocyclic carbene 7

Figure 7.Resonance structure of methoxymethylcarbene 8

Figure 8.HOMO and LUMO of electrophilic and nucleophilic carbenes 8

Figure 9 .Matrix isolation scheme 10

Figure 10.Matrix isolation instrument 11

Figure 11.Photoaffinity labeling scheme 12 xiii

Figure 12 .Reactivity of singlet versus triplet carbene 14

Figure 13 .Trapping reaction of HCl and O 2 in low temperature matrices 14

Figure 14 .Possible intermediates, 4, 5 and 6 proposed from rearrangement of 3 19

Figure 15 .Azacycloheptatetraene 11 19

Figure 16 .1-Naphthylcarbene (39 ) 26

Figure 17 .Bicyclic intermediates from vinyl carbene 36

Figure 18 .Rearrangement of vinylcarbene to cyclopropene 36

Figure 19 .Conformers of vinylcarbene 37

Figure 20 .C6H7N potential energy surface 45

Figure 21.Possible rearrangement of furylcarbenes, 99 and 115 50

Figure 22.Resonance structure of furyl and thienylchlorocarbene 99 and 121 51

Figure 23 .Possible rearrangement products 127 and 128 of thienylcarbene 121 53

Figure 24 .Resonance structure of methylenecyclopropene 160 59

Figure 25 .Seven membered cyclic allenes generated from aryl carbenes 60

Figure 26 .Possible electronic configuration of planar allene 61

Figure 27 .Theoretical study of cyclic cumulenes, aryl vs heteroaryl 67 xiv

Figure 28 .Isodesmic study of 188 and 194 71

Figure 29 .C=C=C angle of 188 and 194 72

Figure 30 .HCl addition product of 188 and 194 73

Figure 31 .B3LYP calculated energies of benzothienyl vs benzofuryl system 73

Figure 32 .B3LYP calculated energies of benzoxzolyl vs benzofuryl system 76

Figure 33 .Ketenimines 199 and 204 77

Figure 34 .Geometric comparision of 194 vs. 208 80

Figure 35 .B3LYP predicted energies of CF 3 and benzothienylchlorocarbene 81

Figure 36.Retrosynthesis of trifluoromethyldiazirine 85

Figure 37. Benzothienyl carbenes 206 and 224 87

Figure 38 .Crystal structure of ketone 227 89

Figure 39 .E and Z conformer of 3-benzothienyl(CF 3)oxime 228 89

Figure 40.3-Benzothienyl(CF 3)diaziridine 230 90

Figure 41. UV-vis of 2-benzothienyl(CF 3)diazirine 205 92

Figure 42.UV-vis of 3- benzothienyl(CF 3)diazirine 223 92

Figure 43.Geometry of 2- and 3- benzothienyl(CF 3)diazirine 94 xv

Figure 44.HOMO and LUMO of 2- and 3- diazirine 95

Figure 45 .Twisted diazirines discovered by the Sheridan group 96

Figure 46. Top: Matrix isolated IR spectrum of 3-benzothienyl(CF 3)diazirine ( 223 ); bottom: B3LYP 6-31+G** predicted IR spectrum of diazirine 223 97

Figure 47 . Top: B3LYP 6-31+G** predicted IR spectrum of syn carbene 224a; middle:

difference IR spectra of diazirine 223 converting into carbene syn carbene 224a; bottom:

B3LYP 6-31+G** predicted IR spectrum of diazirine 223 98

Figure 48 . B3LYP 6-31+G** IR spectrum of anti singlet carbene 224 99

Figure 49 . B3LYP 6-31+G** predicted IR spectrum of anti triplet carbene 224 99

Figure 50 . B3LYP 6-31+G** predicted IR spectrum of syn triplet carbene 224 100

Figure 51 . Solid line: Matrix isolated UV-vis spectra of diazirine 223 and carbene 224 ;

solid bars: TD B3LYP 6-31+G** UV-vis spectra of diazirine 223 and carbene 224 101

Figure 52 . Top: B3LYP predicted IR spectra of carbene 224b ; middle: difference IR

spectra showing syn carbene 224a going away and anti carbene 224b growing; bottom:

B3LYP predicted IR spectra of syn carbene 224a 102

Figure 53 . Solid line: Matrix isolated UV-vis spectra of syn carbene 224a (blue), and anti

carbene 224b (black); solid bars: TD B3LYP 6-31+G** predicted UV-vis spectra of syn

carbene 224a (blue), and anti carbene 224b (black) 103 xvi

Figure 54 . Top: B3LYP predicted IR spectra of benzylic chloride 231 ; middle: difference

IR spectra showing carbene 224 going away and benzylic chloride 231 forming; bottom:

B3LYP predicted IR spectra of carbene 224 104

Figure 55 . Top: B3LYP predicted IR spectra of bicyclic intermediate 232 ; middle:

difference IR spectra showing carbene 224 going away and bicyclic intermediate 232 forming; bottom: B3LYP predicted IR spectra of bicyclic intermediate 232 107

Figure 56 . Solid line: Matrix isolated UV-vis spectra of bicyclic intermediate 232

(black), and carbene 224 (red and blue); solid bars: TD B3LYP 6-31+G** predicted UV-

vis spectra of bicyclic intermediate 232 108

Figure 57 . Top: B3LYP predicted IR spectra of ring-opened carbene 233 ; middle: difference IR spectra showing bicyclic intermediate 232 going away and ring-opened carbene 233 forming; bottom: B3LYP predicted IR spectra of 232 109

Figure 59 . Solid line: Matrix isolated UV-vis spectra of ring-opened carbene 233 (black), and methylenecyclopropene 235 (red); solid bars: TD B3LYP 6-31+G** predicted UV- vis spectra of ring-opened carbene 233 and methylenecyclopropene 235 112 xvii

Figure 60 . Solid line: Matrix isolated UV-vis spectra of intermediates 232, 233 and 234

(black), solid bars: TD B3LYP 6-31+G** predicted UV-vis spectra of intermediates 232

(black), 233 (red) and 234 (blue) 113

Figure 61. Top: B3LYP predicted IR spectra of ring-opened carbene 233; middle: difference IR spectra showing methylenecyclopropene 235 going away and ring-opened carbene 233 forming; bottom: B3LYP predicted IR spectra of methylenecyclopropene

235 114

Figure 62.Matrix isolated IR spectrum of deuterated 3-diazirine (223i ) 116

Figure 63.Top: B3LYP 6-31+G** predicted IR spectrum of deuterated carbene 224i;

middle: difference IR spectra of deuterated diazirine 223i converting into carbene 224i; bottom: B3LYP 6-31+G** predicted IR spectrum of diazirine 223i 117

Figure 66 .B3LYP predicted energies of 2- and 3-carbenes, 206 and 224 and their

rearranged products 121

Figure 67 .Cumulenes characterized by the Sheridan group, 123

Figure 68 .Predicted nitrogen containing cumulene 124

Figure 69 .2- and 3- position hydrogen’s in an indole 237 125

1 Figure 70. H NMR of 2- and 3-indolyl(CF 3)ketone 126

Figure 71 .Solid line: Matrix isolated UV-vis spectrum of N-methyl-2- indolyl(CF 3)diazirine (244 ); solid bars: TD B3LYP 6-31+G** predicted UV-vis spectrum

of diazirine 244 127

Figure 72 .Top: B3LYP predicted IR spectrum of diazirine 244 ; bottom: matrix isolated

IR spectrum of diazirine 244 130

Figure 73 . Top: B3LYP predicted IR spectra of syn carbene 245a; middle: difference IR

spectra showing diazirine 244 going away syn carbene 245a forming; bottom: B3LYP predicted IR spectra of diazirine 244 131

Figure 74 .B3LYP predicted IR spectra of syn and anti carbene 245a and 245b 132

Figure 75 .Solid line: Matrix isolated UV-vis spectrum of N-methyl-2- indolyl(CF 3)carbene (245); solid bars: TD B3LYP 6-31+G** predicted UV-vis spectrum

of carbene 245 133 xix

Figure 76 .Top: B3LYP predicted IR spectra of quinoimine 246 ; middle: difference IR spectra showing syn carbene 245a going away and quinoimine 246 forming; bottom:

B3LYP predicted IR spectra of syn carbene 245a 134

Figure 77. Solid line: Matrix isolated UV-vis spectra of carbene 245 (red) and quinoimine

246 (black); solid bars: TD B3LYP 6-31+G** predicted UV-vis spectra of quinoimine

246 135

Figure 78 .Top: B3LYP predicted IR spectra of syn carbene 245a; middle: difference IR

spectra showing quinoimine 246 going away and syn carbene 245a forming; bottom:

B3LYP predicted IR spectra of quinoimine 246 136

Figure 79 .Top: B3LYP predicted IR spectra of syn quinoimine 246b ; middle: difference

IR spectra showing anti quinoimine 246a going away and syn quinoimine 246b forming; bottom: B3LYP predicted IR spectra of anti quinoimine 246a 137

Figure 80 .B3LYP predicted energies of carbene 245 and its rearranged products 138

Figure 81 .Possible mechanism for formation of zwitterions 236b and 247 139

Figure 82 .B3LYP predicted IR spectrum of 236b 140

Figure 83 .TD B3LYP predicted UV-vis spectrum of 236b 140

Figure 84 .B3LYP predicted IR spectrum of 247 141

Figure 85 .TD B3LYP predicted UV-vis spectrum of 247 141

Figure 86 . 2- and 3-indolyl(CF 3)ketone 249 and 250 143

Figure 87 .Resonance structure of tosyloxime 256 146

Figure 88 .Matrix isolated UV-vis of diazirine 259 148

Figure 89 .Top: B3LYP predicted IR spectra of syn carbene 260a ; middle: difference IR

spectra showing diazirine 259 going away and carbene 260 forming; bottom: B3LYP predicted IR spectra of diazirine 259 150

Figure 90 . Solid line: Matrix isolated UV-vis spectra of diazirine 259 (red) and carbene

260 (black); solid bars: TD B3LYP 6-31+G** predicted UV-vis spectra of diazirine 259

(red) and carbene 260 (black) 151

Figure 91 .Difference IR spectra showing 2089 cm -1 and 2016 cm -1 bands 153

Figure 92 .B3LYP predicted IR spectra of syn and anti conformer of

methylenecyclopropene 154

Figure 93 .B3LYP predicted energies of carbene 260 and possible rearrangement products 156

Figure 94 .Resonance structure of carbene 260 156

Figure 95 .B3LYP predicted energies of carbenes 224 and 260 and their possible

rearrangement products 157 xxi

Figure 96 . Top: B3LYP predicted IR spectra of carbene 203 ; middle: difference IR spectra showing diazirine 202 going away and carbene 203 forming; bottom: B3LYP predicted IR spectra of diazirine 202 (A. Nikitina, unpublished results) 160

Figure 97 . Top: B3LYP predicted IR spectra of ketenimine 204 ; middle: difference IR spectra showing carbene 203 going away and ketenimine 204 forming; bottom: B3LYP predicted IR spectra of carbene 203 (A. Nikitina, unpublished results) 161

Figure 98 . Matrix isolated UV-vis of diazirine 202, carbene 203, and ketenimine 204 (A.

Nikitina, unpublished results) 162

Figure 99 .Top: B3LYP predicted IR spectra of syn and anti diazirine 277a and 277b ; bottom: matrix isolated IR spectrum of diazirine 277 167

Figure 100 .Syn and anti diazirine, 277a and 277b 167

Figure 101.Top: Matrix isolated UV-vis spectrum of diazirine 277 ; bottom: TD B3LYP predicted UV-vis spectra of syn and anti diazirine 277a and 277b 168

Figure 103. Middle: difference IR spectra showing anti diazirine 277b going away after irradiation at 376 nm (10 min); bottom: B3LYP predicted IR spectrum of anti diazirine

277b 171 xxii

Figure 104.Solid line: matrix isolated UV-vis spectra of carbene 278 ; solid bars: B3LYP predicted UV-vis spectra of syn and anti triplet carbene 278 172

Figure 105.Top: B3LYP predicted IR spectrum of ketenimine 279 ; middle: difference IR spectra showing syn and anti carbene 278a and 278b going away and ketenimine 279 growing; bottom: B3LYP predicted IR spectra of carbene 278a and 278b 173

Figure 106.Top: B3LYP predicted IR spectra of ketenimine 279 and quinoimine 280 ; middle: difference IR spectra showing syn diazirine 277a going away and 279 and 280 growing; bottom: B3LYP predicted IR spectrum of syn diazirine 277a 175

Figure 107.Matrix isolated UV-vis spectrum of ketenimine 279 176

Figure 108 .Difference IR spectra of ketenimine 279a and 279b 177

Figure 109 .B3LYP predicted IR spectra of carbonyl oxide 281 and dioxirane 282 180

Figure 110. B3LYP predicted energies of carbene 278 and 202 182

Figure 111. Matrix isolated IR spectrum of benzoxazolyl(CF 3)diazirine (288 ) 186

Figure 112. Top: B3LYP predicted IR spectra of syn and anti

benzoxazolyl(CF 3)diazirine 288 ; bottom: matrix isolated IR spectrum of 288 188

Figure 113. Matrix isolated UV-vis spectrum of benzoxazolyl(CF 3)diazirine (288 ) 189

Figure 114.B3LYP predicted IR spectra of syn and anti diazirine 288 189 xxiii

Figure 115. Difference IR spectra of benzoxazolyl(CF 3)diazirine (288 ) going away at

334nm (5min) and new products forming 190

Figure 116. B3LYP predicted IR spectrum of benzoxazolyl(CF 3) triplet carbene, both syn

and anti conformer, 289a and 289b 191

Figure 117 .Experimental UV-vis spectrum after irradiation of diazirine 288 192

Figure 118. TD B3LYP predicted UV-vis spectra of syn and anti

benzoxazolyl(CF 3)carbene 289a and 289b 192

Figure 119. Top: B3LYP predicted IR spectrum of quionimine 290 ; middle: difference IR spectra showing carbene 289 going away and quionimine 290 forming; bottom: B3LYP predicted IR spectra of carbene 289 194

Figure 120 . Solid line: Matrix isolated UV-vis spectra of quinoamine 290 ; solid bars: TD

B3LYP 6-31+G** predicted UV-vis spectra of quinoamine 290 195

Figure 121. B3LYP predicted IR spectra of keteinimine 291 196

Figure 122.TD B3LYP predicted UV-vis spectra of keteinimine 291 197

Figure 123. Difference IR spectra after irradiation of diazirine 288 at 334nm 197

Figure 124. B3LYP predicted energies of benzoxazolyl(CF 3)carbene 289 and benzoxazolyl(Cl)carbene 197 and their rearrangement products 200

Introduction

Carbenes are reactive intermediates having neutral divalent carbon atoms. The

carbon atoms of carbenes have only six electrons in their valence shells. Out of the

six electrons, four electrons are used to make two sigma bonds and two electrons

remain as non-bonding electrons. Carbenes can be either singlet or triplet based on

the spin of these two non-bonded electrons. If the unshared electron spins are paired,

a carbene is a singlet, and if the electron spins are parallel, it is a triplet (Figure 1).1

Figure 1. Singlet and triplet carbenes.

Understanding the electronic states and substitution effects on carbenes is vital to exploring and modifying the synthetic and practical applications of carbenes. Controlling the electronic states of carbenes attached to aryl and heteroaryl systems has influenced the applications of carbenes in the materials, synthetic and pharmaceutical sectors. 2-5 To study, understand, and explore carbenes attached to five membered heterocycles,

Sheridan’s group has reported observation and characterization of several of these carbenes and their photochemical rearrangements at low temperature in inert matrices.

These studies have not only given valuable insights in understanding the electronic and substitution effects of aryl and heteroaryl carbenes, but also have uncovered several 2

exotic reactive intermediates which are unstable at room temperature. Continuing this exploration, we uncovered several novel heteroaryl carbenes, such as those attached to indole, benzothiophene, benzothiazole and benzoxazole. Before we dive into our own work, we will provide a little bit of background on carbenes, especially regarding electronic states, steric effects and reactivity. Since methylene is the archetypical carbene, we will start with reference to :CH 2.

1. Background

1.1 Methylene

The parent carbene, methylene :CH 2, has fascinated chemists for a long time.

The diverse applications and reactivity shown by methylene led researchers to investigate more about the electronic states, geometry and reactivity of this species. The four bonding electrons of methylene’s carbon atom are accommodated in two hybridized valence atomic orbitals, making two σ bonds. The two unshared electrons are

accommodated in two valence atomic orbitals. If the geometry of the carbene is linear,

the two non-bonding orbitals of the carbene would be pure p-orbitals and degenerate,

hence the electronic state of the carbene would be a triplet. But, if the carbene is bent, the

n degeneracy is removed. A bent carbene carbon atom with C 2v symmetry will have one sp orbital, and a pure p-orbital perpendicular to it.

The electronic state of a carbene depends on the electron-electron repulsion energy versus the relative orbital energies of the two unshared electrons. The relative energies of 3

the σ and π orbitals thus dictate the ground state multiplicity of carbenes. It has been suggested that if the σ to π separation is larger than 2eV, the carbene will be a ground state singlet, and if the separation is less than 1.5 eV, then it will be a ground state triplet

(Figure 2).1

Figure 2 : Relationship between carbene geometry and frontier orbitals.

The above discussion implies that the geometry of the carbene and the spin states

are closely related. The geometry, spin state, and the energy gap between σ and π orbitals of methylene were topics of interest and investigation for a long time. Herzberg reported the spectra of methylene in his attempts to study the spectra of polyatomic radicals. 6-8

Based on the electronic spectra obtained, Herzberg postulated that methylene has two low lying states, triplet and singlet. 7 He suggested that triplet is the ground state and has a

linear or nearly linear geometry, whereas singlet is bent with a 103 o bond angle.

However, EPR spectra obtained from separate low temperature matrix experiments

conducted by Bernheim and Wasserman gave a non- zero E/hc value indicating that

triplet methylene has a non-linear geometry. 8 Re-analysis of Herzberg’s electronic 4

spectra data revealed that in fact triplet methylene has a non-linear geometry. The carbene bond angle of bent triplet methylene was first proposed to be 134 o by Bunker and

Jensen. 9 Ab-initio calculations later predicted 137 o for bent triplet methylene and 102 o for singlet methylene. 10,11 Similarly, the singlet- triplet energy gap of methylene was

investigated both theoretically and experimentally. Both experimental and calculational

results suggest that triplet methylene is 8-10 kcal/mol lower in energy than singlet

methylene (Figure 3). 12

Figure 3 . Methylene singlet and triplet energy levels.

The electronic states of carbenes can be changed by increasing the energy gap between the σ and π orbitals. Changing the geometry of the carbene central carbon atom 5

can change the energy gap between the σ and π orbitals. Also, substituting H with

electron donating ligands raises the π orbital energy, hence increasing the energy gap

between σ and π orbitals. Finally, inductive electron withdrawing effects by ligands can lower the σ orbital energy, increase the energy gap between σ and π orbitals, and stabilize

the singlet state relative to triplet. 13,14

1.2 Stability and substitution effects

It is well known that substituents with lone pairs stabilize singlet states of carbenes relative to triplet states. For example, chlorocarbene, dichlorocarbene, methoxychlorocarbene and dimethoxycarbene are singlet carbenes. In chlorocarbene, the singlet is 6 kcal/mol lower in energy than triplet. Stabilization of singlet is attributed to the resonance structure shown in Figure 4. Furthermore, in methoxy carbene the singlet is

20 kcal/mol lower in energy than triplet because oxygen is a better π donor than halogens. 15

Figure 4 . Resonance stabilization of singlet methylenechlorocarbene.

On the basis of a perturbation orbital diagram, the substituents interacting with π orbitals of an adjacent carbene center can be classified as a) π electron donors such as –

NR 2, -OR, -SR, - F, -Cl, -Br and –I; b) π electron acceptors such as –COR, -SOR, -

SO 2R, -NO and –NO 2; c) conjugating groups such as alkene, alkyne and aryl (Figure

5).1,13,14,16

The π electron donor groups raise the p π orbital energies and hence raise the energy gap between σ and π orbitals leading to ground state singlet carbenes. Whereas, π acceptors such as alkenes, alkynes and aryl either leave the energy gap between σ and π the same or lower the energy gap, giving ground state triplet carbenes. 1,13,14

Figure 5 . A carbene p-orbital interacting with (a) π electron donors

(b) π electron acceptors , and (c) a conjugating groups. 1, 13

Contrary to initial beliefs that carbenes are always very unstable and reactive, carbenes substituted with strong electron donors such as N can be stable at room 7

temperature. The first stable carbene, phosphino silyl carbene, was reported by Bertrand’s group in 1988. 1 Similarly, imidazol-2-ylidene was reported in 1991. Today, there are many stable singlet carbenes reported in the literature. 1,14 All of these carbenes are

stabilized by the adjacent heteroatom substituents (Figure 6).

Figure 6. N-heterocyclic carbene.

1.3 Philicity of carbenes

Beside spin state, the reactivity of carbenes is also governed by their philicity.

The philicity of carbenes has been studied by measuring the relative rates (selectivities) of cyclopropanation of electron rich and electron poor alkenes. 1, 17 Carbenes behave as amphibilics, that is both as electrophiles and nucleophiles, depending upon the electronic density of their substituents. Studies have showed that CBr 2 and CCl 2 preferentially react with more highly substituted alkenes, suggesting these carbenes are electrophilic. 1

Meanwhile, CH 3OCCH 3 reacts preferentially with less substituted alkenes, displaying strong nucleophilic selectivity toward electron poor alkenes.1 Lone pair 8

donation from the oxygen atom to the carbene p orbital induces the nucleophilicity in the carbene as shown in the resonance structure in Figure 7.18

Figure 7. Resonance structure of methoxymethylcarbene.18

The molecular orbitals of the alkene addition transition state show that the HOMO

of the alkene and the LUMO of the carbene (electrophilic), and the LUMO of alkene and

the HOMO of the carbene (nucleophilic) interact (Figure 8).

Figure 8. HOMO and LUMO of electrophilic and nucleophilic carbenes.1

Based on the above transition state (T.S) MO diagram (Figure 8), both CCl 2 type

and CH 3OCCH 3 type carbenes can react with electron rich alkenes and electron poor

alkenes. If a carbene reacts preferentially with electron rich alkenes then it is known as 9

electrophilic and if a carbene reacts preferentially with electron poor alkenes, then is known as nucleophilic.

1.4. Observation and characterization

Methods to directly study reactive species that have short lives under ambient temperatures are very limited. The reactive species either have to be observed very quickly, immediately after their formation, or must be trapped cold and studied spectroscopically. Carbenes are generally generated by thermal or photochemical extrusion of nitrogen from diazirines or diazo compounds. The most common techniques used to investigate carbenes spectroscopically are laser flash photolysis(LFP) and matrix isolation .1

Porter and Norrish were awarded the 1967 Nobel Prize for the development of the

flash photolysis method. In laser flash photolysis, the carbene precursor is hit with a short

pulse of light, from millisecond to femtosecond, to generate carbenes which are detected

by a probe beam. LFP provides kinetic information, and in more recent developments,

even spectroscopic details of the carbenes. 1

Matrix isolation in general refers to experimental techniques in which guest species (molecules, atoms, ions, etc) are trapped in rigid host materials. The host materials can be a crystalline solid, a polymer or a glass formed by freezing a liquid or solidifying a gas. Solvents such as ether-pentane-alcohol (EPA), methyltetrahydrofuran

(MTHF), or a mixture of CFCl 3 and CF 3Br become transparent on freezing and are viable

for spectroscopic studies. These days, the term matrix isolation is used mainly to refer to 10

the trapping of guest particles in a solidified inert gas (N 2, argon, neon, etc.) at low temperatures (around 10 K) (Figure 9). This technique was first introduced around the

1950s by Pimentel (Figure 10).19-21 Typical matrix isolation experiments include the guest species being diluted in an inert gas (usually nitrogen or argon) and then deposited onto a cold window as low as 4 K, and studied using various spectroscopic techniques such as IR, UV-vis and EPR spectroscopy. The trapped molecules cannot undergo any bimolecular reactions since they are prevented from diffusing.

Figure 9 . Matrix isolation scheme.1,22 11

Figure 10. Matrix isolation instrument.

Density Functional Theory (DFT) calculations are extensively used in our work to study and characterize the carbenes and related intermediates. 23,24 Experimental results and theoretical results are compared, supplemented by trapping reactions, to identify the electronic states of carbenes and to get structural information on the generated photoproducts. Details of matrix isolation techniques will be discussed in the experimental section.

1.5. Applications

Carbenes play a vital role in synthetic chemistry, both organic and inorganic. 25,26

The intermediacy of carbenes is proposed in many reaction mechanisms pathways. One of the most common reactions is cyclopropanation. Carbenes have been widely studied in soot formation, combustion, magnetic materials, fullerene productions and interstellar chemistry. 27 Carbenes (arylcarbenes) play major roles in photoaffinity labeling agents 2,3,28 12

and have been reported in more diverse settings such as materials cross-linking. 4 A recent

publication discusses applications of carbenes to prepare hydrophobic coatings. 5 Some of

these applications will be discussed later.

1.5.1. Photoaffinity labeling

Photoaffinity labeling is widely used to identify the binding sites in enzymes or receptors. A photoaffinity label is a substrate with a photolabile group attached. Once the probe binds to the desired enzymes or receptors, the substrate is irradiated to produce a reactive species which chemically derivatizes the enzyme or receptors (Figure 11). The most commonly used photolabile groups are azides, diazirines and benzophenones.2,3,28

Figure 11. Photoaffinity labeling scheme.

The ideal photoaffinity labeling agent possesses the following characteristics. (a) stable at ambient experimental temperature and for storage purposes, (b) precursors easy to synthesize, (c) efficient photolysis and should be wavelength selective (>300 nm) so that irradiation won’t damage proteins and amino acids, (d) should generate highly 13

reactive intermediates, and (e) generated reactive intermediate should form stable compounds with receptors.

Also photoaffinity labeling is preferred over chemical affinity labeling because the photoaffinity ligands are neutral and are preferred for carrying out preliminary experiments. Furthermore, the photoaffinity labeling agents are more controllable and form reactive intermediates such as carbenes upon photolysis. Aryl azides, though explosive, are easier to synthesize and were used as photoaffinity labeling reagents starting 1969. Diazoacetyl compounds are also used as labeling agents. The drawbacks of diazoacetyl compounds are they are reactive even in the dark with protein functional groups and unstable at low pH. Compared to diazo compounds, diazirines are chemically and thermally more stable. Aryl diazirines are also stable to dilute acids, oxidizing agents, and mild reducing agents such as sodium borohydride. Nonetheless, diazirines too have drawbacks. Photolysis of diazirines can form unwanted byproducts besides carbenes, such as diazo compounds. Unsubstituted alkyl diazirines rearranges to olefins after forming carbenes and halo diazirines may form labile products as a result of carbene reacting with trapping reagent, so these diazirines are not suitable for labeling.

1.6. Reactivity of carbenes

The reactivity of singlet and triplet carbenes is different. Singlets react in a concerted fashion and are stereospecific, whereas triplets react in a stepwise manner, and are non-stereospecific (Figure 12).1 14

Figure 12 . Reactivity of singlet versus triplet carbene.

1.6.1 Addition

Trapping reactions in low temperature matrices are used to study and characterize electronic states of carbenes. For instance, singlet carbenes react with HCl to give addition products whereas triplet carbenes react with molecular oxygen to give carbonyl oxides, and irradiation of the carbonyl oxides generate dioxiranes (Figure 13). 29,30

1 H Cl 35K CF3 CF3 HCl H3CO H3CO

3 O O O O H CO h 3 35K H CO H3CO CF3 3 CF3 CF3 O2 16 Figure 13 . Trapping reaction of HCl and O 2 in low temperature matrices. 15

1.6.2. Rearrangement

Rearrangement reactions of carbenes are particularly exotic, both in terms of mechanism and products formed. The term rearrangement in carbenes is somewhat ambiguous too. Insertion of a carbene into an adjacent sigma bond is called 1, 2 rearrangement. On the other hand, insertion of a carbene into a more remote bond is termed as an intramolecular insertion and similarly intramolecular addition is a term frequently used for addition of a carbene to a double bond.26,31

Carbenes can rearrange, for example, via ring formation, ring expansion, ring

contraction and ring opening. Rearrangements of carbenes can be initiated thermally or

photochemically and play important roles in synthetic applications. Reversible

interconversion reactions between divalent carbenes and their rearranged tetravalent

photoproducts have been studied and monitored spectroscopically in inert matrices.

Here, we will review various intramolecular rearrangements of carbenes (especially aryl

and heteroaryl carbenes) at low temperatures.

1.7. Phenylcarbene

Halo and alkyl substitution on methylene affects the electronic states and reactivity of carbenes. The effect of π donation and inductive electron withdrawing groups increases the σ–π orbital energy gap of carbenes. So, the obvious question to ask

is what would be the effect of aryl substitution? 16

Perhaps, phenylcarbene is the most widely investigated carbene beside methylene.

Phenylcarbenes have wide synthetic applications giving clean carbene adducts in high yield and can react efficiently with alcohols, alkanes and alkenes. 32 Spectroscopic studies of phenylcarbene were published most recently in 2000 by Matzinger and Bally,33 and

theoretical studies were published in 2011 by Cavallotti and co-workers. 34

Scheme 1 . Thermolysis of phenyl diazomethane 1 to heptafulvalene 2

The intermediacy of phenyl carbene was proposed in the gas phase reaction of

phenyltosylhydrazone salt to heptafulvalene by Stouw et al. 35,36 Hedaya et al . reported that vacuum pyrolysis of phenyldiazomethane 1 produced heptafulvalene 2(Scheme 1).37

Several intermediates and mechanisms were proposed for the formation of 2.31,38 The intermediacy of phenyl carbene 3 was unanimously accepted, but the rearrangement

mechanism for the formation of heptafulvalene 2 was a hot topic and received attention

from theoreticians and experimentalists. 31,33

Scheme 2 . Thermolysis of phenyl diazomethane 1

The initial explanation was that phenylcarbene 3 rearranges to cycloheptatrienylidene 4 by ring expansion and then cycloheptatrienlidene 4 dimerizes into heptafulvalene 2 (Scheme 2). Later, the possibility of formation of cycloheptatetraene 5 was also proposed. 39 Similarly, Jones et al . showed that pyrolysis of all isomers of tolyldiazomethane generated styrene and benzocyclobutene. 38 The bicyclic intermediate was also proposed as a ring closing intermediate from phenyl carbene which then ring expands to cycloheptatrienylidene (Scheme 3).36,38,40

Scheme 3 . Bicyclic product 6 proposed as an intermediate to 4 and 5

After numerous experimental and theoretical studies, it was concluded that

phenylcarbene 3 is a ground state triplet, and it has a bent geometry around the carbene

center. Triplet phenylcarbene behaves as a benzyl radical, which suggests that triplet

phenylcarbene is planar and has an extended π system. 41,42 The EPR spectrum of

phenylcarbene 3 was reported in the 1960s by Wasserman and co-workers and shows zero-field parameters D=0.5098 cm -1, E=0.0249 cm -1. D is an estimation of the average distance between the unpaired electrons, which gives information about the delocalization of conjugated π systems. E is an estimation of the difference of magnetic

dipole interaction along x and y axes. The ratio D/E is used to estimate the bond angle at

the carbene center. 43 18

Scheme 4 . Matrix isolation study of phenyldiazomethane 1 and phenyldiazirine 8

In an attempt to study, observe and characterize phenyl carbene and its

rearrangement products, Chapman’s group generated phenylcarbene 3 by thermolysis and

photolysis and studied it in low temperature matrices. Spectroscopic observation and

characterization by IR and UV-vis of phenylcarbene 3 in an inert gas matrix was reported

in 1982 by the Chapman group. Phenylcarbene 3 was generated by irradiation of its precursor phenyldiazomethane 1 and confirmed by trapping reaction with carbon monoxide, which generated ketene 9 (Scheme 4). Further irradiation of phenylcarbene 3 gave a new product. The identification and characterization of this product was not straightforward. In the beginning, this new product was suggested to be either ring expanded cycloheptatetraene (allene) 5, cyclopropene 6 or ring extended carbene 4

(Figure 14). 39 19

Figure 14 . Possible intermediates, 4, 5 and 6 proposed from rearrangement of 3.

The ring expanded carbene 4 was ruled out because the trapping reaction with CO did not generate a ketene. A bicyclic intermediate 6 was also ruled out from a deuterium

study and also the IR did not show bands around 1750 cm -1 expected for 6. The allene 5 was considered as a possible product, as the IR showed bands around 1816 cm -1 close to its nitrogen analogue 11 (Figure 15), and also warming the matrix containing product to room temperature generated a product with m/z=180, a dimer 2. The allene 5 was confirmed by Chapman and co-workers experimentally by generating from different precursors such as 14 , 15 and 16 in low temperature matrices (Scheme 5, 6). Isotope labeling studies were conducted to confirm the allene 5.42 So, the possibility of formation of ring expanded carbene 4 was ruled out experimentally.

Figure 15 . Azacycloheptatetraene 11 .

The complete characterization of phenyl carbene 3 and cycloheptatetraene 5 by

UV-vis and IR spectroscopy was reported by Matzinger and Bally in 2000. 33 The authors

42 also reported theoretical calculations of the C7H6 energy surface.

Scheme 5 . Matrix isolation study summary of phenylcarbene 3

Scheme 6. Thermal dimerization of 5 to 2 via 17

1.7.1. Investigation of C 6H7 potential energy surface

Bally and coworkers’ reports of 1996 and 2000 theoretically and experimentally confirmed Chapman’s results that phenylcarbene 3 is a ground state triplet and the intermediate involved is the allene 5 not the ring expanded carbene 4.33,44 Bally and co-

workers assigned and discussed the spectra using CASSCF/CASPT2 excited- states and

B3LYP 6-31G (d) level calculation. The experimental IR spectrum of phenylcarbene 3 does not fit with the calculated IR spectrum and the authors explain this to be due to the anharmonicity of the Ph-C-H bending mode. But the experimental spectrum of allene 5 matches well with the calculated spectrum. 22,33 The calculated singlet-triplet gap in

phenylcarbene 3 is 4 kcal/mol.45,46 Bicyclic product 6 is believed to be the intermediate in

the conversion of phenyl carbene 3 to allene 5.42

Theoretical calculations 44,47,48 show that cycloheptatetraene 5 has a distorted

allenic structure and is lower in energy on the C 7H6 energy surface compared to phenylcarbene 3, bicyclic intermediate 6 and the cycloheptatrienylidene 4. Ground state

triplet phenylcarbene 3 is the next lowest in energy. The bicyclic intermediate 6 and

singlet phenyl carbene 3 are nearly degenerate in energy. The ring opening of bicyclic

intermediate 6 into allene 5 has a low activation energy barrier which supports the 22

experimental conclusion of the formation of allene 5 photochemically.33 Recently, in

2011, Cavallotti and co-workers reported the “Analysis of the Reactivity on the C 7H6

Potential Energy Surface”. 34 This report shows that the exploration of phenyl carbene 3 is

still ongoing.

1.7.2. Phenylchlorocarbene

Sheridan and Ganzer reported the synthesis of phenylchlorodiazirine and its matrix isolation study in a 10 K argon matrix. 29 Contrary to phenylcarbene 3, phenylchlorocarbene 18 is a ground state singlet. The change in spin multiplicity is attributed to lone pair π donation and σ electron withdrawal by the chlorine. 49 Similar to

phenylcarbene 3, phenylchlorocarbene 18 also ring expands to give cycloheptatetraene 19

photochemically (Scheme 7). The IR spectroscopy of phenylchlorocarbene 18 resembled

that of phenylcarbene 3, but the UV-vis spectra was different. Though irradiation of

phenylchlorocarbene 18 generated the ring expanded product cycloheptatetraene 19 , the

rate of the photochemical conversion of phenylchlorocarbene 18 was slower than

phenylcarbene 3.

Scheme 7 . Phenylchlorocarbene 18 rearrangement to allene 19

Singlet carbenes do not react with oxygen, in general. But, annealing the oxygen doped phenylchlorocarbene 18 matrix at 35 K generated carbonyl oxide 21 , which slowly gave dioxirane 23 , benzoyl chloride 22, and ozone on irradiation. Further irradiation of the dioxirane 23 gave phenylchloroformate 24 , chlorobenzene 25 and carbon dioxide

(Scheme 8).29

Scheme 8 . Trapping reaction of phenylchlorocarbene 18 with O 2

1.7.3. Tolyl carbenes

Thermolyses of isomeric tolyldiazomethanes 26 , 27 and 28 yield styrene 29 and

benzocyclobutene 30 (Scheme 9).38 This interesting outcome generated an enormous

interest in the mechanisms behind these transformations. To understand and study the

reactive intermediates and rearrangement of tolylcarbenes, Chapman’s group generated

and studied tolyldiazomethanes in low temperature matrices.50

Scheme 9 . Thermolysis of tolyldiazomethanes 26, 27 and 28

H H H

N2 N2 N2

H3C CH3 26 27 CH3 28

-N2 -N2 -N2

29 30

Chapman and McMahon showed that the isomeric tolylcarbenes present an intriguing array of carbene rearrangements via ring expansion, hydrogen shift and carbene-to-carbene transformations. 50,51

Scheme 10 . Tolylcarbenes rearrangement 50

30 31

H H H

H C CH3 3 33CH 34 32 3

CH3 CH3

36 37 CH3 35

CH3

29 38

On irradiation, para 32 , meta 33 and ortho-tolyl 34 carbenes generated the allenes

35 , 36 and 37 in low temperature matrices, whereas the ortho tolylcarbene 34 gave the hydrogen shift product, quinomethide 31 also in addition to allene (Scheme 10).

Although the ring-expanded carbene 4 is proposed to go through bicyclic intermediate 6, direct observation or characterization of either the bicyclic intermediate 6 or the ring expanded carbene 4 from phenylcarbene 3 is not reported yet. Mistaken reports were published claiming the spectra of ring expanded carbene 4 which were proven to be of 26

different species. 52 Until today, both of these species 4 and 6 have not been generated

from phenylcarbene 3 even in low temperature matrices.

1.8. Naphthylcarbenes

The naphthylcarbenes 39 and 40 are benzoanalogues of phenylcarbene 3. Trozzolo and

co-workers reported the EPR spectrum of 1- naphthylcarbene ( 39 ) in 1965. 53

Figure 16 . 1-Naphthylcarbene (39 ).

Rotation of the aryl-carbene bond gives rise to two conformers of carbene, s-E 39a and

s-Z 39b (Figure 16). Steric hindrance with hydrogen at the 8-position of naphthalene with hydrogen at the carbene center results in s-E conformer being 1 kcal/mol lower in energy than s-Z. The estimated barrier for rotation of s-E 39a and s-Z 39b is greater than 4.5-6.3 kcal/mol.54

Since then, both 1- and 2-naphthylcarbenes were investigated by pyrolysis, solution trapping and at low temperatures. Gas phase studies of atomic carbon reactions with 27

naphthalene 40, and of naphthyldiazomethanes 41 and 42, resulted in the formation of cyclobuta(de)naphthalene ( 43) (Scheme 11).

Scheme 11 . Flash vacuum pyrolysis of 1- and 2- naphthyldiazomethane 41 and 42

Mechanistically, C-H insertion of 1-naphthylcarbene (39) results in cyclobuta-

(de)naphthalene ( 43) . Since pyrolysis of both naphthyldiazomethane, 41 and 42, resulted in the formation of same product at higher temperature, interconversion between 1- and

2- naphthylcarbene ( 39) and ( 44) was proposed and investigated. 55 56 Several solution

trapping studies demonstrating interconversion between naphthyl carbenes 39 and 44 and

rearrangement products, 45 , 46 , 47 and 48 have been reported (Scheme 12). 57

Scheme 12 . Reaction scheme for possible interconversion of 1- and 2-naphthylcarbenes 39 and 44

Contrary to phenylcarbene 3, where a bicyclic intermediate 6 was never observed or characterized, naphthylcarbene rearrangement is entirely different and interesting.

Observation and spectroscopic characterization of bicyclic intermediates of both 1- and

2- naphthylcarbene in low temperature matrices was first reported by McMahon and

Chapman in 1986. 58 Precursor diazo compounds of both 1- and 2- isomers, 41 and 42 , were generated from tosyl hydrazine salts. Photolysis of 1- naphthyldiazomethane ( 41) with >510 nm light for 16 h in a 15 K, argon matrix produced 4, 5-benzobicyclo-

[4.1.0]hepta-2,4,6-triene ( 46) and cyclobuta(de)naphthalene ( 43). 1- Naphthylcarbene

(39) was not observed or characterized spectroscopically. Similar results were obtained for 2-isomer 42 too. Irradiation of 2-naphthyldiazomethane ( 42) with >364 nm light 29

generated 2, 3-benzobicyclo[4.1.0]hepta-2,4,6-triene ( 48). 2-Naphthyl carbene ( 44) was not observed or characterized. McMahon and Chapman claimed that they generated a ring expanded product 45 , which was not verified (Scheme 13). 58

In contrast, pyrolysis of both 1- and 2–naphthyldiazomethane ( 41) and ( 42 ) and

cocondensation with argon generated cyclobuta(de)naphthalene ( 43) as major product

and bicyclic products 46 and 48 were not observed.

Scheme 13 . Matrix isolation study of naphthyldiazomethane 41 and 42

Although existence of naphthylcarbenes was shown by EPR and solution trapping, other spectroscopic characterization of naphthylcarbenes was only reported in

1993 by the McMahon group. 59-61 Irradiation of 2-naphthyldiazomethane ( 42) in a 10 K

Ar matrix generated 2-naphthyl carbene ( 44) which was photochemically converted to bicyclic intermediate 48 (Scheme 14). No evidence of either ring expanded product 45 or

interconversion of 2-naphthyl carbene ( 44 ) to 1-naphthyl carbene ( 39) was observed. 30

Scheme 14 . Photochemical interconversion of 2-naphthylcarbene 44 into bicyclic intermediate 48

N2 N N H H

42 49

>300nm Ar, 10K

360nm or 560nm H

290nm 44 48

Six years later, in 1999, the McMahon group reported the spectroscopic characterization of 1-naphthylcarbene ( 39) generated from both diazo compound 41 and

diazirine 50 in 10 K argon matrices (Scheme 15).

Scheme 15 . Photochemical interconversion of 1-naphthylcarbene 39 into bicyclic product 46

In the case of both 1- and 2-naphthyl, the carbene and bicyclic intermediate were

photochemically interconvertible. 57,62 But the direct observation and characterization of benzocycloheptatrienylidene 47 and benzocycloheptatetraene 45 were not reported untill early 2000. 63 Also, evidence of formation of 47 and 45 were still unclear. The formation

of cyclobuta(de)naphthalene ( 43) from both the isomers of naphthalene suggests that

rearrangements should occur between 1- and 2- naphthyl-carbenes ( 39) and ( 44). So, the

McMahon group studied a series of precursors in low temperature matrices to understand the mechanisms of interconversion of naphthylcarbenes and rearranged intermediates such as bicyclic intermediate, ring expanded carbene and ring expanded allene. 64 32

Scheme 16 . Spectroscopic evidence of benzocycloheptatetraene 45 in low

temperature matrices

Direct spectroscopic evidence of a benzocycloheptatetraene 45 and a benzocyloheptatrienylidene 47 were reported by McMahon’s group. Thermolysis of tosylhydrazone salt 51 gave diazo compound 52 which was directly co-deposited in an argon matrix. Broadband irradiation (λ>237, λ>472, or λ>571 nm) of diazo compound generated the benzobicycloheptatetraene 45 in argon matrices in 10 K (Scheme 16). The experimental IR matched the calculated IR spectra (B3LYP 6-31G*) very well.

Irradiation of the allene 45 at short wavelengths, λ>237, gave weak signals of 2- naphthylcarbene (44) which was characterized by UV-vis and EPR spectroscopy . 61

Scheme 17 . Matrix isolation study of benzodiazocycloheptatriene 53

McMahon and coworkers reported the photochemistry of benzodiazo- cycloheptatrienes 53 and 54 in low temperature matrices. Irradiation of 4, 5-

benzodiazocycloheptatriene ( 53) at λ >613 nm at 10 K in an argon matrix gave 2,3- benzobicyclo[4.1.0]hepta-2,4,6-triene ( 48) and small amounts of triplet 4,5-benzocyloheptatrienylidene ( 47) and 2-naphthylcarbene ( 44). The 2-naphthylcarbene ( 44) and

bicyclic product 48 photochemically interconverted (Scheme 17). Similarly, irradiation of

2, 3-benzodiazocycloheptatriene (54) at λ >613 nm generated 4, 5-benzobicyclo-

[4.1.0]hepta-2,4,6-triene ( 55). The carbene, 2, 3-benzocyloheptatrienylidene ( 47), was not observed. Irradiation of bicyclic product 46 at λ=290 nm generated triplet 1-

naphthylcarbene (39) which photochemically interconverted with bicyclic intermediate

46 (Scheme 18). 61 34

Scheme 18 . Matrix isolation study of benzocycloheptadienyldiazomethane 54

Although the McMahon group was able to generate and characterize intermediates proposed in naphthyl carbene rearrangements, direct spectroscopic evidence of interconversion of 1- and 2- naphthyl carbene in low temperature matrices is still unclear.

1.8.1. Naphthylchlorocarbenes

The effect of halogen substitution in naphthylcarbenes was studied by the

Sheridan group. Contrary to parent naphthylcarbenes, the naphthylchlorocarbenes are ground state singlets.65 Sheridan and Rempala reported the first direct characterization of

1-naphthylchlorocarbene (57 ) by IR and UV-vis spectroscopy in low temperature

matrices.65 Irradiation of 3-chloro-3-(1-naphthyl)diazirine (56) with 366 nm light

generated 1-naphthylchlorocarbene ( 57). Prolonged irradiation of carbene 57 at 366 nm

generated a new species. The new species matched the calculated IR for the bicyclic

product 58 which is consistent with the parent naphthylcarbene. The bicyclic product 58

and carbene 57 were photochemically interconvertible (Scheme 19).65

Scheme 19 . Matrix isolation study of 1-naphthylchlorodiazirine (56)

Sheridan and Rempala also reported the photochemistry of 2-naphthylchlorocarbene 60 . In the case of 2-naphthylchlorodiazirine ( 59) irradiation with 366 nm light generated the 2-naphthyl carbenes, both s-Z and s-E isomers. Irradiation of the carbenes at 436 nm converted the s-Z isomer into s-E isomer. Prolong irradiation of the carbenes at 366 nm generated the bicyclic product 61 (Scheme 20). So, both 1- and 2- naphthylchlorocarbene rearrange into bicyclic product and interconvert photochemically. 65

Scheme 20 . Matrix isolation study of 2-naphthylchlorodiazirine (59)

1.9. Vinylcarbenes

The bicyclic intermediates proposed in phenylcarbene and characterized in naphthyl-carbenes are related to rearrangement of vinylcarbenes (Figure 17).

Figure 17 . Bicyclic intermediates from vinylcarbene.

Though aryl carbenes have been extensively studied spectroscopically,

spectroscopic characterization of vinylcarbenes are few. 66-69

Figure 18 . Rearrangement of vinylcarbene to cyclopropene.

Observation of parent vinyl carbene 62 via EPR was first reported by Wasserman and co-workers in 1974 (Figure 18).66 The vinyl carbene 62 was generated from the 37

photolysis of vinyldiazomethane in a matrix. The generated carbene 62 was a ground

state triplet and two similar but unidentical EPR signals indicated the presence of two

isomeric forms ( 62a and 62b ) of vinyl carbene (Figure 19).66

Figure 19 . Conformers of vinylcarbene.

Though synthetic utility and role of singlet vinyl carbenes in thermal and photochemical cyclopropene isomerization was known, spectroscopic information about singlet vinyl carbene was nonexistent till early 2004. Observation and characterization of singlet vinyl carbenes and their photochemical transformations in nitrogen matrices at 8

K were reported by Zuev and Sheridan in 2004. 70 Photolysis of chloro diazirine 64 at 385 nm generated both conformers of carbene 65. Contrary to parent vinyl carbene 62 , the chloro substituted vinyl carbenes 65 are singlet ground states. Irradiation of carbenes 65

at 578 nm generated cyclopropene 66 and allene 67 (Scheme 21).

Scheme 21 . Matrix isolation study of singlet vinylchlorocarbene 65

N N Cl H H H H R 385nm H Cl H 578nm Cl C R Cl H R N2, 8K H R H R N2, 8K H Cl 64 65a 65b 66 67

R=H,CH 3 38

Sheridan and Zuev also reported the observation and characterization of cyclic singlet vinyl carbenes. 70 The carbene 69 was generated by the photolysis of

corresponding diazirine 68 in nitrogen matrices. Irradiation of the vinyl carbene 69 at 585

nm destroyed the carbene and an intense peak at 1751 cm -1 was generated in an IR spectrum, which corresponds to bicyclic product 70 . The ring-expand product 71 was not observed (Scheme 22). 70

Scheme 22 . Matrix isolation study of cyclopentylchlorodiazirine 68

1.10. Heteroarylcarbenes

Mechanistic and theoretical studies of aromatic carbenes and their electronic states are well understood. But the study of heteroarylcarbenes and their electronic states and reactivities is still ongoing. 71

1.10.1 Pyridylcarbenes

Carbenes attached to nitrogen containing 6-membered rings were initially explored by Crow and Wentrup. 72 Pyrolysis of triazolopyridine 72 produced azobenzene

73 and aniline 74 . The major product was azobenzene 73 which suggested that the

pyridylcarbene 75 rearranges into phenylnitrene 76 which then dimerizes into azobenzene

73 (Scheme 23).41,73 39

Scheme 23 . Interconversion of pyridylcarbene 75 and phenylnitrene 76

In 1978, Chapman’s group reported the photochemistry of phenyl azide 77 in an

argon matrix. 73 Irradiation of phenyl azide 77 at 8 K in an argon matrix generated aza-

cycloheptatetraene 78 which was characterized by IR spectroscopy. Irradiation of phenyl

azide 77 in an EPR spectrometer generated the phenylnitrene 76 , but they did not observe

phenylnitrene 76 by IR spectroscopy. The known intense X, Y transition of triplet phenyl

nitrene 76 with zero-field parameters D= 1.027 cm -1, E= 0 cm -1 was observed. Continued

irradiation of the sample produced a new signal with zero-field parameters D= 0.537 cm -

1, E= 0.027 cm -1which is very close to phenylcarbene 3, D= 0.5098 cm -1, E= 0.0249 cm -1.

The similarity in the EPR signal suggested that the new product formed might be 2- pyridylcarbene (75). To confirm this prediction, the Chapman group studied the photolysis of triazolopyridine 72 in an argon matrix. Irradiation of triazolopyridine 72

generated 2-pyridyldiazomethane ( 79) in an argon matrix which upon further irradiation generated the 2-pyridylcarbene (75), which was characterized by EPR. Further irradiation 40

of the product generated a new product whose signal matched the EPR of phenylnitrene

76. Thus the photochemical conversion of phenylnitrene 76 into 2-pyridylcarbene (75) was confirmed in low temperature matrices (Scheme 24).41,73

Scheme 24 . Matrix isolation study of pyridylcarbene interconversion

N N3

N CHN 2 77 78 79

3 3 N N N N N CH 72

76 75

3 N 3 CH 80 CH

N 84 N 85

CHN 2

N N N 81 83 82

Chapman’s group also studied the photochemistry of 3- and 4-diazomethylpyridine in argon matrices.74 Irradiation of 4-diazomethylpyridine (81) gave a new product with EPR signals of D=0.533 cm -1, E= 0.0248 cm -1which was assigned to 4- pyridylcarbene (84). Further irradiation of the product generated 3-pyridylcarbene ( 85) 41

with signals of D= 0.513 cm -1, E=0.0241 cm -1, 2-pyridylcarbene (75), and phenylnitrene

76 . Similarly, irradiation of 3-diazomethylpyridine (82) generated 3-pyridylcarbene (85),

4-pyridylcarbene (84), and phenylnitrene 76 . The EPR signals of all isomeric pyridylcarbenes were distinguishable from one another. When the products formed after photolysis of 3- and 4-diazomethylpyridine were monitored by IR spectroscopy, the product observed and characterized was ring expanded ketenimine 83 , from both precursors. Further irradiation of the product generated the ketenimine 78 obtained from a photolysis of phenylazide 77 and 2-diazomethylpyridine (79). This shows that photochemical interconversion occurs between the isomeric pyridylcarbenes and phenylnitrene (Scheme 25). 73

Scheme 25 . Rearrangment of pyridylcarbene and phenylnitrene

CH CH

N N N 84 83 85

N N CH 76 75 78

Bicyclic intermediates were not observed from the rearrangement of either phenylnitrene 76 or pyridylcarbenes, however the pyridylcarbenes 84 and 85 were

characterized by IR spectroscopy. The carbenes 84 and 85 were trapped with 1.5% 42

carbon monoxide generating the ketenes. The ketenimine 83 when irradiated generated a

new compound which they proposed as an ylide 86 , based on strong IR peak at 1935 cm -

1. Chapman’s group postulated the link between 3-pyridylcarbene (85) and 2-

pyridylcarbene (75 ) (Scheme 26).

Scheme 26 . Cyclic ylide 86 postulated as a possible link between carbenes 85 and 75

It is interesting to look at the geometry of these two species, 83 and 86 . The ketenimine 83 and the zwitterion 86 are both twisted from planarity, but the zwitterion 86 is twisted differently.

Later on, Wentrup and co-workers 75 reported that the cyclic ylide 86 is not the

product observed spectroscopically after the irradiation of ketenimine 83 . They reported

that the irradiation of 3-pyridylcarbene (85) generates two products, via IR spectroscopy.

One product they identified as ring expanded allene 83 which was similar to the product

generated from 4-pyridylcarbene 84 . The other product they characterized as ring-opened

acetylenic nitrile ylide 87 absorbing at 1930 cm -1 in the IR spectra. Pyridylcarbenes (2-,

3- and 4-) undergo both thermal and photochemical rearrangement into pheylnitrene 76

(Scheme 27). 75-78

Scheme 27 . Wentrup matrix isolation study of pyridylcarbenes rearrangement

The Wentrup group generated the deuterated 3-pyridylcarbene ( 93 ) from diazo compound 92 . Irradiation of deuterated carbene 93 produced a cleaner IR spectrum, with

minor ring-expanded product 94 and more of the ring-open product 95 (Scheme 28). The

experimental IR spectrum matched nicely with a calculated spectrum and the deuterium

isotope shifts in the IR spectra, confirming the ring-opened product. 75 44

Scheme 28 . Matrix isolation study of deuterated 3-pyridylcarbene (93)

1.10.2. Investigation of C 6H7N potential energy surface

A relevant partial potential energy surface for C6H7N was calculated using the

B3LYP 6-31G* method. The ketenimine 78 was found to be lowest in energy (Figure

20).75 Though a bicyclic intermediate was proposed as the intermediate in the

rearrangement of pyridylcarbenes to ring expanded ketenimines, spectroscopically it was

elusive.

Figure 20 . C6H7N potential energy surface calculated B3LYP 6-31G*.

1.10.3. Naphthylnitrenes

Wentrup and co-workers have also explored nitrenes attached to naphthalene.79,80

Photolysis of 1- and 2- naphthyl azides, 97 and 98 generated 1- and 2- naphthylnitrenes,

(99 ) and ( 100 ) in low temperature matrices. 79,81 Both nitrenes, 99 and 100 upon irradiation generated the bicyclic intermediate azirines 101 and 104 , which were 46

characterized spectroscopically via IR spectroscopy. The authors also reported the spectroscopic characterizations of cyclic nitrile ylides or zwitterions 103 and 106 in low temperature matrices (Scheme 29). 79,81

Scheme 29 . Matrix isolation study of naphthylazides 97 and 98

Thus, the bicyclic intermediates such as 89 and 90 were not observed in phenylnitrene 76 rearrangement, but their benzoanalogs 101 and 104 were observed and

characterized in naphthylnitrene rearrangement, paralleling the contrast between phenyl

and naphthylcarbenes. 77

1.10.4. 5-Membered heteroarylcarbenes

Carbenes attached to 5-membered heterocycles are important because of the synthetic utility of 5-membered heterocycles in organic syntheses, materials chemistry and astrochemistry.1,82 Also, workers have found that carbenes attached to 5-membered rings behave very differently than aryl carbenes. 71,83-87 47

Rearrangement of 2-furylcarbene (109 ) was first reported in 1971 by Hoffman and Shecter. 88 Pyrolysis of furyldiazomethane 108 generated from tosyl salt 107 produced 2-pentene-4-ynal ( 110 ) ( 110a =Z-81% and 110b =E-19%). The proposed intermediate 2-furylcarbene (109 ) was not observed or characterized spectroscopically.88

However, thermolysis of furyldiazomethane 108 in the presence of cyclooctane and styrene produced trapping products 111 and 112 respectively indicating the generation of

2-furylcarbene ( 109 ) (Scheme 30)89

Scheme 30. Pyrolysis and trapping reaction of furyldiazomethane 108

Later in 1979, Shevlin and Dyer reported that they were also able to generate the

Z -2-pentene-4-ynal (110a) from the reaction of atomic carbon with gaseous furan. The atomic carbon was generated by the pyrolysis of 5-diazotetrazole (113) (Scheme 31). 85

Scheme 31.Carbon addition reaction of furan

Shevlin’s experimental results were consistent with Shecter’s findings that 2- furylcarbene ( 109 ) is generated in the ring-open process, but the authors were not able to get spectroscopic evidence of furylcarbene 109 .85

The low temperature matrix study of furyldiazomethane 108 was first reported by

Albers and Sanders in 1997. 87 Albers and Sander were able to deposit 2- furyldiazomethane ( 108 ) in an argon matrix at 10 K and carry out its photolysis at 435 nm. 87 After irradiation of the diazo compound 108 , the generated new product was characterized spectroscopically as the ring- open Z-2-pentene-4-ynal ( 110a ). The ring- opened product isomerizes from the Z (110a ) to E (110b ) isomer photochemically at

>385 nm. But, the furylcarbene 109 was not observed or characterized even in low temperature matrices (Scheme 32).

Scheme 32 . Matrix isolation study of furyldiazomethane 108

A 2-furylchlorocarbene (115) was later observed and characterized for the first time in 1998 by Sheridan and Khasanova in low temperature nitrogen matrices.83 49

Scheme 33 . First observation and characterization of furylchlorocarbene 115

Irradiation of 2- furylchlorodiazirine (114 ) at 404 nm in an N2 matrix at 8 K

generated both anti (115a ) and syn (115b ) isomers of singlet 2-furylchlorocarbene

(115 ). 83 The carbene 115 was characterized spectroscopically via IR which matched

closely with the calculated (MP2/6-31G*) IR spectra. Irradiation of the carbenes at

> 404 nm in N 2 matrix at 8K generated s-cis-aldehyde-acetylene 116a . Careful

irradiation of the aldehyde-acetylene 116a isomerized it into the s-trans conformer

116b . Contrary to parent furylcarbene 109 , which is a ground state triplet,

furylchlorocarbene 115 is a ground state singlet. 83

In both the parent case and in chloro substituted furylcarbene, two other possible intermediates from carbene, ring-closed bicyclic product 117 and ring-expansion carbene

118 (Figure 21), were not observed or characterized either under pyrolysis or photolysis conditions.

Figure 21. Possible rearrangement of furylcarbenes, 99 and 115 .

Molecular orbital analysis and transition state studies of furylcarbene 109 and similar moieties were conducted by Herges. 90 Herges indicated that ring opening of 2-

furylcarbene ( 109 ) should be a six-electron thermally allowed process that he termed a

“coarctate” process. 90,91 In 2000 Birney, however, reported that ring opening of furyl

carbene 109 has “pseudopericyclic” orbital topology not “coarctate” orbital topology. 92

When heteroatoms are involved in the coarctate type concerted reactions, where an in- plane lone pair interacts with the in-plane sigma bond thus resulting in making and breaking of bonds, this rearrangement is termed as “pseudo pericylic ”. 92,93 According to

Birney, the transition state of the furylcarbene 109 rearrangement proceed through a

planar transition state but with a symmetry induced disconnect in the orbital topology.

So, the “pseudopericyclic” reactions go through planar transition states, but they are

neither aromatic nor antiaromatic as they lack the loop of interacting orbitals. 90,93

Experiments similar to furyl were conducted to study the thienyl system also.

Scheme 34 . Thermolysis and solution trapping reactions of the diazomethane 120

In the thiophene system, Shechter and co-workers found out that the pyrolysis of

2-thienyl diazomethane (120 ) gave dimers, trans and cis ethylene compounds, 123 and

124 beside the ring opening product 122 (Scheme 34).94 The additional products 123 and

124 obtained in thiophene case were not observed in the furan case. This might be due to, compared to oxygen, sulfur probably slows ring opening and hence dimers were obtained. Resonance structures of furylcarbene 99 and thienylcarbene 121 are shown in

figure 22. The trapping reactions of tosyl salt 120 gave products 125 and 126 similar to

the furyl case. 95

Figure 22. Resonance structure of furyl and thienylchlorocarbenes 99 and 121 . 52

Sander and Albers conducted low temperature matrix isolation studies of the thiophene system also. Photolysis of thienyl diazomethane 120 at > 435 nm in an argon matrix generated the ring opening products, Z 122a and E 122b . Products 122a and 122b were photochemically interconvertible (Scheme 35). 96

Scheme 35 . Matrix isolation study of thienyldiazomethane 120

Similar to furyl, the ring opening of thienylcarbene is facile and considered as a pseudopericyclic reaction. Recently McMahon and coworkers repeated the photolysis of

2-furyl 98 and 2-thienyl 120 diazomethanes in argon matrices at 10 K and reproduced same results but were unable to observe and characterize carbenes either in IR or in UV- vis spectroscopy. 71

Once again, from both the thermolysis and photolysis experiments of thienyl diazomethane 120 , either the bicyclic product 128 or the ring-expand product 127 were

not observed or characterized in low temperature matrices (Figure 23).

Figure 23 . Possible rearrangement products 127 and 128 of thienylcarbene 121 .

Unpublished results from Wang, Nikitina and Sheridan show that irradiation of 2- thienylchlorodiazirine ( 129 ) at 404 nm in N 2 matrices at 10 K generates thienylchlorocarbene 130 . Irradiation of carbene 130 at 578 nm produced ring-opened product

131 . Irradiation of 131 at 366 nm generated a new product along with carbene 130b. The new product was characterized as strained cumulene 132. Further irradiation of cumulene

132 makes a new product which was characterized as 134 (Scheme 36). Contrary to parent thienylcarbene 121 , which is calculated to be ground state triplet, thienylchlorocarbene 130 is a ground state singlet.

Scheme 36 . Spectroscopic observation and characterization of thienylchlorocarbene

130

Contrary to carbenes attached to the 2-position of 5-membered heterocyclic rings, studies on carbenes substituted at the 3-position of 5-membered heterocyclic rings are fewer. 86,97,98 The 3-substituted carbenes do different photochemistry than 2-substituted

carbenes. Pyrolyses of 3-furyldiazomethane ( 137 ) and 3-thienyldiazomethane ( 138 ) were

studied by Shechter and co-workers in 1978. 97 Diazo compounds were generated by the

pyrolysis of tosyl hydrazone salts 135 and 136 which gave the corresponding dimers 141 and 142 for furyl and thienyl systems respectively. Trapping with cyclooctane and

diphenyl ethylene gave trapping products 142-145, consistent with intermediates

generated from carbenes (Scheme 37). 55

Scheme 37 . Thermolysis of 3-furyl and 3-thienyldiazomethane 137 and 138 respectively

In 1997, Sander and Reinhard reported the photochemistry of 3-furyldiazomethane ( 137 ) and 3-thienyldiazomethane ( 138 ) in low temperature matrices.

Irradiation of the diazo compounds at 435 nm produced rearranged methylene- cyclopropenes 148 and 149. The authors reported that they were not able to observe or

characterize either the carbenes 139 or 140 , nor the proposed bicyclic intermediates 146

and 147 in either the furyl or thienyl case.86,87 They mention a vibration around 1650 cm -1 indicative of a possible bicyclic intermediate 147 in the thienyl case. In the case of furyl,

irradiation of the methylenecyclopropene 148 at 350 nm caused it to ring-open into

aldehyde acetylene 150a and 150b (Scheme 38) . 56

Scheme 38 . Matrix isolation study of 3-furyl and 3-thienyldiazomethane 137 and 138 respectively

Khasanova and Sheridan published the observation and characterization of a 3- furylcarbene (152) for the first time in 1999.98 Irradiation of 3-furylchlorodiazirine ( 151) at 366 nm in nitrogen matrices at 10 K generated anti singlet 3-furylchlorocarbene

(152a). Furthermore, irradiation of anti carbene 152a at 578 nm generated the syn isomer

152b and the process was reversible at 366 nm generating anti carbene 152a. Irradiation

of the carbene 152 generated the rearranged product, methylenecyclopropene 154 . The

bicyclic product 153 , proposed to be the intermediate in the formation of methylenecyclopropene 154 from carbene 152 , was not observed. Annealing a N 2 matrix containing carbene 152 doped with HCl at 35 K generated the HCl addition product 155 , which is one of the characteristics of singlet carbene (Scheme 39). Contrary to parent 3- furylcarbene ( 139 ) which is a triplet ground state 3-furylchlorocarbene ( 152 ) is a ground state singlet. 57

Scheme 39 . Spectroscopic observation and characterization of 3-furylchlorocarbene

152

Recently, in 2012, McMahon and co-workers reported matrix isolation studies of

3-furyl and 3- thienyldiazomethane (137 ) and (138 ), respectively.71 In the 3-furyl case, irradiation of 3-furyldiazomethane ( 137 ) at > 571 nm generated both isomers of

methylenecyclopropene 148, which on further irradiations at λ> 330 nm generated ring-

opened product 150 . Neither carbene 139 nor bicyclic intermediate 146 was observed or

characterized. However, EPR, IR and UV-vis spectroscopy of 3-thienyl carbene (140 )

was reported, along with spectroscopic evidence of an intermediate tentatively assigned

as bicyclic product 147, generated from 3-thienylcarbene 140 . Irradiation of 3-

thienyldiazomethane ( 138 ) at >534 nm in an argon matrix at 10 K generated both syn and

anti isomers of carbene (140a and 140b ), (s-Z)-methylenecyclopropene 149a and

bicyclic intermediate 147 . Further irradiation of generated products at > 444 nm produced methylenecyclopropene 149a and bicyclic intermediate 147 .

Methylecyclopropene 149a photochemically interconverted into s-E-isomer 149b at 58

λ>363 nm. Irradiation of methylenecyclopropene 149 at λ> 330 nm resulted in ring-

opened product 156 . Overall, in the thienyl case McMahon and co-workers were able to

characterize carbene 140 and show some evidence of bicyclic product 147 (Scheme

40). 71

Scheme 40 . Spectroscopic observation and characterization of 3-thienylcarbene 140

In an unpublished results by Sheridan and Khasanova, the photochemistry of 3- benzofurylchlorodiazirine (157 ) was explored (Scheme 41).

Scheme 41 . Spectroscopic observation and characterization of 3-benzofuryl-

chlorocarbene (158)

Irradiation of 3-benzofurylchlorodiazirine 157 at 366 nm in N 2 matrices at 10 K

generated syn and anti isomers of carbene, 158a and 158b . Continued irradiation at 366

nm generated a new product. The experimental IR spectrum matched closely with the

calculated IR spectrum of methylenecyclopropene 160 . The stability of 160 can be

attributed to its resonance structure (Figure 24).

Figure 24 . Resonance structure of methylenecyclopropene 160 .

1.11. Cyclic Cumulenes

Photochemical rearrangements of aryl and heteroarylcarbenes generate highly strained cumulenes in seven membered rings (Figure 25).

Figure 25 . Seven membered cyclic allenes generated from aryl carbenes.

These strained reactive intermediates are hard to synthesize and are very unstable at room temperature. Studies of aryl and heteroarylcarbenes have opened the possibility to observe and study spectroscopic details and reactivities of strained cumulenes.

Chapman and other workers’ revelation that cycloheptatetraene, or a cyclic allene, can be observed and characterized in low temperature matrices introduced the opportunity to study and characterize these highly reactive species in low temperature matrices.

Continuing that, the Sheridan group work on generation and spectroscopic characterization of cumulenes strained in six membered heterocyclic rings have given valuable information about their reactivity, geometry and electronic state. Strain energy in cyclic structures is one of the determining factors for reactivity. Incorporation of consecutive double bonds in cyclic structures increases the strain energy and hence the 61

reactivity. 99 Because of the deformation of normal bond and dihedral angles, cyclic cumulenes increases angle strain as the ring size decreases. As the ring size decreases, the cyclic cumulene is forced to planarity. Johnson showed that the electronic configuration of allenes change on constraining into small rings; with the possibility of diradical or zwitterion character (Figure 26). 99

Figure 26 . Possible electronic configuration of planar allene.

1.11.1. 1, 2-Cyclohexadiene

The existence of 1,2 cyclohexadiene ( 164 ) was demonstrated by Witting and

Fritze in 1966. 100 Dimer 165 was generated when 1-bromocyclohexene was treated with

KOtBu in dimethylsulfoxide. The attempt to generate and characterize 164 62

spectroscopically in low temperature matrices was reported by Wentrup et al. (Scheme

42). 101 Flash vacuum pyrolysis of bicyclo[3.1.0]hexane-6-carbonyl chloride ( 161 ) generated ketene 162 which loses CO to generate carbene 163 . The authors claimed that carbene 163 ring opens to produce cumulene 164 based on 1886 cm -1 peak in an IR

spectrum. However, Wentrup later mentioned in personal communication that the result

was not reproducible and it was not cumulene 164 .

Scheme 42 . Wentrup matrix isolation study to characterize cumulene 164 spectroscopically

Sander et al. reported the matrix isolation study of bromo(triethylstannyl) compound 166 in an argon matrices (Scheme 43).102 Flash vacuum pyrolysis of 166

followed by isolation of the generated product in an argon matrix at 10 K, gave an IR

spectrum showing an absorption at 1865 cm -1 which was assigned to cumulene 164 . But later, it was found that the 1865 cm -1 peak was from trimethylstannane and not from cumulene 164 .102

Scheme 43 . Sander matrix isolation study to characterize 164 spectroscopically

1.11.2 Cumulenes from heteroarylcarbenes

The intermediacy of a heterocumulene in six membered ring was proposed by

Emanuel and Shevlin in the atomic carbon reaction with pyrrole. 103

1.11.2.1 Atomic carbon reaction

In 1994, Emanuel and Shevlin reported the mechanism of the reaction of atomic carbon with pyrrole. 103 They cocondensed atomic carbon with pyrrole (166 ) at 77 K and after warm up they were able to obtain and characterize pyridine (170 ). They proposed the intermediate involved in this reaction is the bicyclic product 167 which rearranges

into a species better described as a dehydropyridinium ylide 168 rather than as an allene

169 . Isotopic labeling studies with 13 C and deuterated methanol suggested the intermediacy of the novel dehydropyridinium ylide 168 (Scheme 44). MP2/6-31G* level

calculations predicted 168 as lower in energy, and 169 was not a stationary point on the 64

C5H4N potential energy surface. They further confirmed their findings with N-methyl- pyrrole.

Scheme 44 . Atomic carbon reaction with pyrrole (166 )

Similarly, Shevlin and co-workers also reported in 1997 the sulfur analogs in the

atomic carbon reaction with thiophene. Unlike pyrrole, the thiophene system was

complex and formed several products. Isotope labeling studies and trapping reactions

suggested that in the case of thiophene the intermediate formed is an allene 173 rather than zwitterion 174 . Also, MP2/6-31G* level calculation found a stationary point for

173 .104 The products obtained after the reaction were 176a, 176b and 177. Trapping

reactions with either HCl or DCl and isotopic labeling were used to conform the reaction

intermediates and the mechanistic pathways (Scheme 45).

Scheme 45 . Atomic carbon reaction with thiophene (171 )

H * * R warmup HCl * * or * + C S S S R=H,D S H S 171 172 173 174 175

H * * S H S S 121c 176a

HCl S * * S S R=H,D S * R C * 178 127c 127b 179

* 171 + C H * S * H S S 121d 176b H *

S H 140c S * S 177

1.11.2.1 Theoretical study of 6-membered allenes

In 2001, McKee et al. reported a computational study of the C 5H4S energy surface. 105 The authors indicated that a plethora of carbene interconversion occurs on the 66

C5H4S energy surface, which was consistent with Shevlin’s experimental work (Scheme

45). The B3LYP predicted energy surface of carbene 140 and some of its rearranged products are shown in Scheme 46.

Scheme 46 . B3LYP 6-31G* calculation of C 5H4S energy surface of some of the possible intermediates

Calculation shows that compared to zwitterion species 180 , cumulene 173 is lower in energy. Also, compared to bicyclic product 147 , 180 is lower in energy and this might be due to aromatic stabilization. High level calculation studies of 6- membered ring allenes were reported by Engels et al. in 2002 (Figure 27). 106 In isobenzene 181 , zwitterion 181c is 28.8 kcal/mol higher in energy than allene 181a , but in didehydropyran

182, the energy difference between allene 182a and zwitterion 182b is only 1 kcal/mol.

Similarly, in isonapthalene the energy difference between allene 183a and zwitterion

183c is 33.7 kal/mol whereas in didehydrochromene the energy difference between allene 67

184a and zwitterion 184b is only 5.4 kcal/mol.106 Their calculations suggest that aromatic

stabilization and heteroatoms significantly lower the energies of cyclic allenes or

zwitterions.

Figure 27 . Theoretical study of cyclic cumulenes aryl vs heteroaryl.

Daoust and co-workers have calculated and compared energies of isodesmic and homodesmic reactions of cyclic allenes to understand better about these strained systems.107 In the case of the 6-membered system, the allenic and total strain energy are the same, 32 kcal/mol, which is understandable for unstrained 6-membered rings. As the 68

ring size decreases, strain energy increases and this is consistent with 1, 2- cyclopentadiene where allene strain contributes 51 kcal/mol out of 55 kcal/mol of total strain energy. Whereas, in 1, 2 cycloheptadiene, allene strain contribute 14 kcal/mol out of 21 kcal/mol of total strain.

1.11.3 Direct observation and characterization of cyclic cumulenes

Benzo analogs of the furyl and thienyl carbenes have been reported by Sheridan’s group, along with the observation and characterizations of several highly strained cumulenes. 84,108-110

1.11.3.1 Direct observation and characterization of didehydropyran

The observation and characterization of a cumulene 188 in a 6-membered ring was reported by Sheridan and Khasanova. 111 In 2000, Khasanova and Sheridan reported

the observation, characterization and photochemistry of 2-benzofurylchlorocarbene

186 .111 The 2-benzofurylchlorocarbene 186 was generated from its corresponding diazirine 185 in 10 K nitrogen matrices. Irradiation of the carbene 186 with 366 nm light generated the first directly observed and characterized 2, 3-didehydro-2H-pyran 188 .111

The irradiation of carbene 186a at 313 nm generated the quinomethide 187 which was photo reversible to carbene 186a at 546 nm. Irradiation of the quinomethide 187 with 366

nm light generated the cumulene 188 which was photoreversible with quinomethide 187 .

Longer irradiation of carbene 186 at 313 nm generated the benzocyclobutadienyl acyl

chloride (Scheme 47).111 B3LYP calculation predicts both carbene 186 and cumulene 188 69

as ground state singlets. Annealing an HCl doped matrix at 30+K generated HCl addition products 189 and 190, from carbene 186 and cumulene 188 respectively , which further

confirmed the singlet ground state of both intermediates.

Scheme 47 . Spectroscopic characterization of cumulene 188 in low temperature matrices

1.11.3.1 Direct observation and characterization of didehydrothiopyran

Nikitina and Sheridan reported the photochemistry of the related 2-

benzothienylchlorocarbene (192 ) in 2005. 84 Carbene 192 was generated from the corresponding diazirine 191 in 10 K nitrogen matrices at 334 nm. Irradiation of the

carbene 192 at 366 nm or irradiation of diazirine 191 at 366 nm generated the cumulene,

194 . Cumulene 194 photochemically converted to carbene 192 at 302 nm. In this case,

however, the ring-opened intermediate 193 was not observed or characterized. Annealing

an HCl doped matrix containing 194 at 25K generated HCl addition product 195 (Scheme

48) .84 Similar to the benzofuryl case, both carbene 192 and cumulene 194 are ground

state singlets.

Scheme 48 . Spectroscopic characterization of cumulene 194 in low temperature matrices

1.11.3 Comparative study of oxo cumulene vs. thio cumulene

B3LYP 6-31 G** studies of isodesmic reactions of the sulfur and oxygen allenes comparing their stabilities were also described by Sheridan and Nikitina. 84 The study showed that the cumulene moiety is more stable in thio case 194 than in oxo case 188 .

Nikitina and Sheridan suggested that because of longer C-S bond and shorter C-S-C angle, sulfur can accommodate an allene-like structure with less strain compared to oxygen (Figure 28).

H H H H H H + Cl + S Cl O Cl H O Cl S H

∆E=8.0 kcal/mol

H H H H H H H H + + S Cl O Cl O Cl S Cl

∆E=6.9 kcal/mol

Figure 28 . Isodesmic study of 188 and 194 .

Calculations showed that the thio cumulene 194 is more twisted than the oxygen system 188 . In thio allene 194 , the C=C=C angle is 131.8°, larger than in oxo allene 188 , where the C=C=C angle is 117.8°. Also in thio allene 188 , the C=S=C angle is 97.8°, smaller than oxo 194, where the C-O-C is 114.6° (Figure 29). These results suggested that the sulfur compound has more allenic character. 72

Another possible reason for stabilization suggested by Nikitina and Sheridan is that aromatic stabilization from any contribution of zwitterionic structure in 194 might be

greater than in 188 . (Note, zwitterionic structures 188b and 194b are transition states).

Nucleus Independent Chemical Shift (NICS) calculation studies of both thio and oxo

allenes as well as the HCl addition products were also reported by Nikitina and Sheridan

(Figure 30). The NICS value in the thio case of HCl addition product 195 is -8.8 and of

zwitterionic form, 194b is -8.4. Corresponding values -7.9 for 190 and -7.4 for 188b were

calculated. Negatives values indicate aromaticity. Similarly for thio allene, 194a, a NICS

value -5.0 and -4.9 ( syn and anti to Cl) and for oxo allene, 188a, -6.6 and -5.7 were

calculated. Compared to the zwitterionic transition states, the allenes have less

aromaticity but still have significant aromatic character. Also, NICS values show that thio

zwitterionic form 194b has more aromatic character compared to oxo allene 188b . But,

the thio allene 194a is deformed more from planarity than oxo allene 188a and is

predicted to have less aromatic character.

Figure 29 . C=C=C angle of 188 and 194 . 73

H H Cl H H Cl O Cl S Cl

190 195

Figure 30 . HCl addition product of 188 and 194 .

An energy chart showing the comparative energies between the benzothienyl and benzofuryl (parenthesis) in chlorocarbene systems is shown in Figure 31. The energy difference between allene and the planar zwitterion in the oxo system is only 2.5 kcal/mol, whereas in the thio system, it is 10.5 kcal/mol.

Figure 31 . B3LYP calculated relative energies of benzothienyl and benzofuryl systems

(benzofuryl in parenthesis). 74

1.11.4 Direct observation and characterization of didehydrobenzoxazine

To further study these exotic molecules, the Sheridan group has generated and studied several ketenimines in 6-membered rings similarly. In 2002, Sheridan and

Nikitina generated, observed and characterized a didehydrobenzoxazine 199 in a novel

carbene- to- carbene transformation in nitrogen matrices at 10 K (Scheme 49).109

Scheme 49 . Spectroscopic characterization of didehydrobenzoxazine 199 in N 2 matrices

Cl N h N N 350nm N N N + 334nm O O Cl Cl O Cl 436nm O 196 10K, N2 197a 197b 198

C C 404nm N N N 366nm 313 Cl O Cl O Cl C 200 O 199a 201

N N

O Cl O Cl 199b 199c

Irradiation of benzoxazolyl diazirine 196 at 334 nm generated the carbene 197 which on further irradiation at 350 nm produced ring opened quinoimine 198 . Irradiation of the quinoimine 198 at 404 nm destroyed the quinoimine bands and generated a new set of bands. The B3LYP calculated IR bands of ketenimine 199 were not a decent match to 75

the experimental IR spectra. But, unrestricted B3LYP calculated IR spectra nicely fit the experimental bands of ketenimine 199 . Interestingly, further irradiation of the ketenimine

199 at 366 nm generated a new set of bands which matched with phenoxy carbene 200 ,

generated by fragmentation of the ketenimine 199 . Finally, irradiation of the phenoxy

carbene 200 at 313 nm generated acid chloride 201 . The fact that the generated

ketenimine only fit UB3LYP singlet calculation hints that the ketenimine has diradical

character, and it looks like 199c more than 199b or 199a .

1.11.4.1 B3LYP energy surface of benzofuran and benzoxazole system

Comparision of calculated energies of the benzofuran and benzoxazole oxygen systems is important to understanding these reactive intermediates. As indicated by the

Sheridan group, didehydropyran 188 shows more allenic character whereas

didehydrobenzoxaxine 199 shows significant diradical character. Compared to carbene,

allene 188 is lower in energy whereas ketenimine 199 is higher in energy than its

corresponding carbene. Ketenimine 199 should be less twisted or deviated from planarity

compared to 188 (Figure 32).

1.11.5 Direct observation and characterization of didehydrobenzothiazine

Unpublished results from Nikitina and Sheridan show the generation of ketenimine 204 from benzothiazolylchlorocarbene 203 . The 2-benzothiazolylchlorodiazirine 202 was synthesized in several steps from the corresponding nitrile. Irradiation of diazirine 202 with 334 nm light in nitrogen matrices at 10 K generated the syn(Cl and

S) 2-benzothiazolylchlorocarbene 203b . 76

Figure 32 . B3LYP calculated energies of benzoxzolyl vs benzofuryl system. 77

Continued irradiation of the matrix at 334 nm or 366 nm destroyed the carbene

203 and generated a new product which was characterized as the ketenimine 204 . The carbene 203 and ketenimine 204 were photochemically interconvertible. Compared to benzoxazole ketenimine 199 , the benzothiazole ketenimine 204 is strikingly different.

Restricted B3LYP predicted IR spectra of 204 matched the experimental IR spectra

satisfactorily, whereas in the benzoxazole case it did not (Scheme 50). The asymmetric

C=C=N stretch in benzothiazole cumulene 204 is 1800 cm -1, whereas for benzoxazole

cumulene 199 is at 1558 cm -1, which suggests more cumulene character in the 204

(Figure 33). Finally, the thio cumulene 204 did not photochemically cleave to an

isonitrile carbene analogous to 200

Scheme 50 . Matrix isolation study of ketenimine 204, A. Nikitina unpublished

results

Figure 33 . Ketenimines 199 and 204 .

1.11.6 Direct observation and characterization of CF 3 didehydrobenzothiopyran

Published and unpublished results from the Sheridan group show that all halogen substituted carbenes and allenes generated from rearrangement of these carbenes are ground state singlets. Contrary to halogens, trifluoromethyl groups are inductively electron withdrawing groups. So, they should have different electronics effects on the neighboring carbenes. Also, all aryltrifluromethyl carbenes reported in the literature were triplet carbenes. To study and investigate the effect of trifluoromethyl group in these systems, Wang and Sheridan studied the matrix isolation photochemistry of 2- benzothienyl (trifluoromethyl)diazirine (205).

Contrary to previous findings that trifluoromethylcarbenes are triplet carbenes,

Wang and Sheridan reported the first singlet state aryl trifluoromethyl carbene in the benzothiophene system.108 2-Benzothienyl(trifluoromethyl)diazirine (205 ) was synthesized following general procedures from 2-benzothienyl(trifluoromethyl)ketone.

Irradiation of 2-benzothienyl(trifluoromethyl)diazirine (205 ) at 404 nm in a 10 K nitrogen matrices generated both conformers of carbene, 206a and 206b . Irradiation of the carbene 206 at 366 nm produced quinomethide 207, which was photochemically interconvertible with the carbene. Furthermore, quinomethide 207 upon irradiation at 436 nm generated cyclic allene 208, which was photochemically interconvertible with ring opened quinomethide 207 (Scheme 51). 79

Scheme 51 . Matrix isolation study of (CF 3) cumulene 208

1.11.7 Trifluoromethyl vs. chloro thiocumulene

Isodesmic reaction calculations by Wang and Sheridan indicate that the trifluoromethyl allene 208 and chloro allene 194 have comparable allenic character and stability (Scheme 52). 108

Scheme 52 . Isodesmic study of cumulene 194 vs 208

o o In CF 3 allene 208a , H and CF3 are twisted 145.6 and 150.4 respectively out of plane

and in the chloro allene 194a ; H and Cl are twisted 156.6 o and 146.4 o. The C=C=C angles

o o for CF 3 and chloro are 134.9 and 131.8 respectively (Figure 34).

Figure 34 . Geometric comparision of 194 vs 208 .

B3LYP predicts singlet carbene 206 is lower in energy than triplet, which was consistent with the spectroscopic and trapping reaction evidence reported by Wang and

Sheridan. Matrix isolated IR and UV-vis spectra best fit prediction for singlet carbene

206 . Also, annealing an HCl doped matrix generated HCl addition product while the

carbene did not react with O 2. The bent cumulene 208a is lower in energy than its zwitterionic transition state structure 208b (Figure 35).

1.12. Applications of heteroarylcarbenes

Carbenes attached to 5-membered ring heterocycles have been postulated in various rearrangements and in the synthesis of complex heterocyclic compounds. Saito and co-workers reported tandem cyclization of diketone 209 , involving furyl carbene

210 as an intermediate, to make furan derivative 211 (Scheme 53). 112 81

Figure 35 . B3LYP predicted energies of CF 3 and Cl benzothienylcarbene and their

rearrangement products.

Scheme 53. Retrocyclization of furylcarbene 210, generated from diketone 209, to

211

In 2009, Cid et al. reported the formation of indolizine 214 from 2-enylpyridine,

212 . In this transformation, the reaction is proposed to go through the intermediate

indolizynyl carbene 213 (Scheme 54). 113,114

Scheme 54. Formation of indolizine 214 from enylpyridine 212 via carbene 213

Smith et al . and L’abbe and coworkers have explored the reactivity of azido- triazoles such as 215, which rearranges into product 216 and after loss of nitrogen,

generates carbene and gives benzene addition product 217 .115 Haley and co-workers have

been exploring the synthetic utility of triazines and ene-ene-yne cyclizations. Compound

218 generates either cinnoline 220 or isoindazole 222 . Product cinnolines are formed via

carbene intermediate 219 , whereas isoindazolines are formed via zwitterion intermediate 83

221 (Scheme 54). 93 These cyclizations have the potential to open synthetic pathways to

prepare unusual heterocyclic compounds. 93,116

2. Research Objectives

Most of the work reported by Sheridan’s group before 2007 revolved around

halogen substituted carbenes. Recently, however, the Sheridan group is working on

generating and studying trifluoromethyl substituted carbenes. The effect of the

inductively electron withdrawing trifluoromethyl group is different than the π donation of halogens. Moreover, the trifluoromethyl carbenes are favored over halogen substituted carbenes as photo labeling agents. 3 Though there is wide application of trifluoromethyl

diazirines as photoaffinity labeling agents, the electronic states and reactivity of

trifluoromethylcarbenes are little known. 117 Observation, characterization and in-depth

study of these species would help to design better labeling agents.

Scheme 55. Ene-ene-eyne cyclization via carbene intermediate

The potential applications of heteroaryl CF3 diazirines in photoaffinity labeling, and the possibility of generating heteroarylcarbenes stable enough to characterize and yet reactive toward intra and intermolecular reactions generating highly strained unusual reactive intermediates, have led us to explore several new heteroaryl substituted CF 3 85

carbenes. We also hoped that we would be able to produce heteroaryl carbenes that could not be previously investigated. Herein, we report some of our recent investigations.

2.1 Trifluoromethyl diazirines

The general retrosynthetic route for synthesis of CF 3 diazirines is shown in Figure

36. Diazirines, three membered rings with N=N, are prepared from oxidation of diaziridines, the saturated counterpart. Diaziridines are prepared by treating tosyl or mesyl oximes with liquid ammonia. Tosyl or mesyl oximes are prepared by tosylation or mesylation of oximes. Both oximes and tosyl or mesyl oximes can have two stereoisomers, E and Z. Oximes are prepared by treating ketones with hydroxylamine hydrochloride and trifluoro ketones are prepared by treating starting material with acylating agents.

Figure 36. Retrosynthesis of trifluoromethyldiazirine.

2.2 3-Heteroarylcarbenes

Rearrangement of 3-thienyl and 3-furyl carbenes (both triplets) form methylene cyclopropenes.71,86,87,98,118 The proposed bicyclic intermediate 146 and 147 have been 86

elusive. Sander reported the observation of a C=C stretching IR vibration at 1681 cm -1 for the cyclopropene ring of the parent bicyclic intermediate 147 at 10 K in an argon

matrix.86 Our group reported on 3-furylchlorocarbene (152 ) (singlet) which also did not

provide any evidence of bicyclic product 153 .110 A recent report by McMahon and co-

workers has presented evidence that they observed the bicyclic product 147 at low

temperatures in the case of 3-thienylcarbene (triplet).71 Computational study by McKee

118 and co-workers in the C 5H4S energy surface revealed a complex “ plethora of carbene

interconversions” centered around 2-thienyl and 3-thienyl carbenes.

Observation and characterization of carbene rearrangement products such as

quinomethide and cumulenes by the Sheridan group suggests that benzo analogues and

their rearrangements products are considerably more stable than furyl and thiophene

84,108,109,111 cases. A recent publication by Song and Sheridan suggests that CF 3 substitution stabilizes singlet carbenes in a small but systematic amount compared to

117,119 triplet carbenes. Stabilization by a benzo ring and CF 3 group may possibly stabilize intermediates enough to observe and characterize “plethora of carbene interconversions products” at low temperatures in the 3-benzothienyl case. Since singlet aryl CF 3 carbenes

may have advantages over triplet carbenes for labeling studies, heteroaryl singlet CF 3 carbenes might open new avenues for photoaffinity labeling studies.

3. Result and Discussion

3.1 3-benzothienyl(trifluoromethyl)carbene

As mentioned earlier, Wang and Sheridan reported that irradiation of 2-

108 benzothienyl(trifluoromethyl)diazirine (205) generated the singlet CF 3 carbene 206 .

The resonance structure of the 2-carbene 206 helps stabilize the singlet state. We felt that,

based on resonances structures, we should see the same effect in the 3-carbene 224 also

(Figure 37).

Figure 37. Benzothienylcarbenes at 2- and 3- positions, 206 and 224 respectively.

Obvious questions were the following: (1) Will 3-benzothienyl (CF 3) carbene be a singlet just like the 2-isomer? (2) Will the rearrangements of the 3-carbene be different than 2-carbene as proposed and observed by previous reports in thienyl cases? (3) More importantly, will we be able to observe and characterize elusive intermediates such as bicyclic product or ring extended carbene in photochemical rearrangements of the carbene? We thus set out to investigate this system. 88

3.1.1 Synthesis of 3-benzothienyl(trifluoromethyl)diazirine

3-Benzothienyl(trifluoromethyl)ketone 227 was synthesized from 3-bromo-

benzothiophene (226) following published procedures. 120,121 Compound 226 was prepared by treating benzothiophene ( 225) with liquid bromine in CCl 4. After work-up with sodium bicarbonate, crude product (containing major 3- and minor 2-bromo isomers) was purified via silica gel column (ethyl acetate: hexane-1:3) and the obtained liquid was further purified via distillation.

3-Benzothienyl (trifluoromethyl) ketone 227 was prepared by slight modification of a procedure reported by Kerdesky and Basha. 121 Compound 226 was treated with t-

BuLi at -78°C in dry ether. The generated lithio precursor was treated in situ with

CuBrMe 2S to make the copper complex, then reacted with TFAA at -78°C and stirred for

12 h at -20°C. The reaction mixture was quenched with saturated ammonium chloride and after work-up the liquid ketone was obtained. The obtained ketone 227 was dissolved in dry ether and left at room temperature, open to air, for several days, to give needle- like crystals. An obtained crystal was used for single crystal X-ray analysis.

Despite the ketone being known, its complete characterization was not available.

It is important to have the correct regioisomer, that is 3-ketone not 2-ketone, to synthesize diazirine at the 3-position. It is very easy to get trifluoroacetic anhydride to react at the 2- position if not careful. So, the 3- trifluoromethyl ketone, 227 was characterized by 1H,

13 C, 19 F NMR, and single-crystal X-ray diffraction (Figure 38). 89

Figure 38 . Crystal structure of ketone 227 .

3-Benzothienyl (trifluoromethyl)oxime 228 was prepared following general methods. The 3-CF 3 ketone 227 was refluxed with hydroxylamine hydrochloride and pyridine in ethanol for 15 h. Workup was done by treating the reaction mixture with 1M

HCl to remove excess pyridine, followed by removing residual solvent. 1H, 13 C and 19 F

NMR spectra showed that the products contained both E and Z isomers with OH peaks at

8.71 ppm and 8.51 ppm (Figure 39). Separation of oxime isomers was unsuccessful by chromatography.

OH HO N N CF3 CF3 R R S S 228a 228b

Figure 39 . E and Z conformer of 3-benzothienyl(CF 3)oxime 228 .

Tosyl oxime 229 was prepared by treating the mixture of oximes with p-TsCl in the presence of triethylamine and a catalytic amount of dimethylaminopyridine, and stirring the reaction mixture at 0 °C for 12 h. After work-up with water, tosyl oxime 229 90

was purified by silica gel column chromatography (ethyl acetate: hexane, 1:8). Only one isomer of tosyl oxime was obtained by 1H, 13 C and 19 F NMR spectra.

Diaziridine 230 was prepared by treating tosyl oxime 229 with liquid ammonia

and stirring at -78°C to -60°C for 18h. Excess ammonia was evaporated by bringing the

reaction mixture to room temperature. Side product amide was washed out with water

and fairly pure diaziridine 230 was recovered. The reaction was monitored by 1H NMR

1 spectroscopy. H NMR (CDCl 3) spectra showed disappearance of tosyl peaks and

appearance of characteristic diaziridine peaks at δ 2.84 and 2.38 ppm. The two NH

protons are diastereotopic and couple to each other (Figure 40).

Figure 40. 3-Benzothienyl(trifluoromethyl)diaziridine 230 .

The final precursor diazirine 223 was obtained after the successful oxidation of

diaziridine 230 with iodine. The prepared diazirine 223 was cleaned by passing through a

silica plug with hexane. The oxidation reaction was monitored both with NMR

spectroscopy and TLC. The diazirine NMR spectra showed clean product with no

diaziridine hydrogen peaks between 2-3 ppm. 1H, 13 C, 19 F NMR spectra of diazirine

were taken and compared with diaziridine for characterization purposes. Special care was 91

taken to make sure the 3-diazirine 223 was not contaminated with 2-diazirine 205 via purification and comparison of 2- and 3- diazirine NMR spectra.

The complete synthetic details of 3-benzothienyl(trifluoromethyl)diazirine (223 ) are shown in Scheme 56.

Scheme 56 . Synthesis of diazirine 223

OH t-Buli O N CF CF3 Br CuBr(Me)2S 3 (CF CO) O Br2 ,CCl4 3 2 NH2OH.HCl R R R R o S 0 C,RT S Ether S Py, EtOH S 12+48 h -78oC to -19oC R=H,D Reflux, 3 h 72% 12 h, 80% 90% H=225 226 227 228 D=225i

O CH3 TsCl, HN NH N N O S Et3N, O N CF3 DMAP Liq. NH CF3 I , Et N CF3 3 2 3 R R MeOH CH2Cl2 CH2Cl2 S S o R 0 C-RT -78oC 0oC, 30 min S 12 h 63% 229 81% 230 223

3.1.2 Twisted diazirines

Besides NMR, a standard tool for major characterization of diazirines is UV-vis spectroscopy. Diazirines typically show characteristic UV-vis n π* absorption between

320-450 nm. The 2-benzothienyl(trifluoromethyl)diazirine (205) is no exception and it shows this characteristic absorption around 380 nm (Figure 41). 92

Absorbance

200 300 400 500 Wavelength (nm)

Figure 41. UV-vis of 2-benzothienyl(trifluoromethyl)diazirine (205 ).

3.5

3.4

3.3

3.2

3.1

2.9

2.8

2.7

2.6

Absorbance 2.5

2.4

2.3

2.2

2.1

1.9

1.8

1.7 200 250 300 350 400 450 500 550 600 650 700 750 800 850 Wavelength [nm]

Figure 42. Matrix isolated UV-vis of 3- benzothienyl(trifluoromethyl)diazirine ( 223 ).

However, the UV-vis spectra of 3-benzothienyl(trifluoromethyl)diazirine (223 ) both in solution and in a matrix, did not show the characteristic n π* transition (Figure

42). Both the 2- and 3-diazirines were studied using density functional theory (DFT) 93

calculations. Time dependent (TD) calculation also showed that, compared to the 2- isomer (403 nm, f=0.04 ), the 3-isomer (437 nm, f=0.007 ) should have very weak absorption in terms of intensities. Thus, the experimental observation of not seeing n π* absorption is somewhat consistent with calculation. We discovered that geometry plays a significant role in terms of the n π* absorption of diazirines. The 3-isomer 223 is twisted

90° compared to general aryl diazirines or compared to the 2-isomer 205 .

Figure 43. Geometry of 2- and 3- benzothienyl(trifluoromethyl)diazirine (205 ) and ( 223)

In the case of the 2-isomer 205, trifluoromethyl group is in plane and the diazirine’s two nitrogen are bisected by the benzothiophene ring, whereas in the 3-isomer

223, the diazirine is sterically forced to be twisted 90° and the N=N is parallel to the ring

(Figure 44). This difference in geometry affects the overall electron density of the 94

HOMO which is very different in the two isomers. In the HOMO of diazirine 205 , the

N=N antisymmetric lone-pair/C-N bond combination overlaps and is strongly mixed with

π-system of the benzothiophene ring. Thus, this mixing of nitrogen lone pair orbitals with aryl ring decreases the HOMO-LUMO gap, hence shifting the “n π*” absorption to the

mid-UV region. The LUMO of 205 is N=N π* in character. In diazirine 223 , however, because the N=N is twisted 90° out of plane, the HOMO is primarily localized on the benzothiophene ring and has very little aryl mixing with the N=N. The π* LUMO of 223 is similar to LUMO of 205 . Hence, the HOMO-LUMO transition in out of plane diazirine

223 is actually a spatially unfavorable aryl- π to diazirine π* transition, with low intensity

(Figure 44). Transitions involving the 223 type diazirines NN lone pair/C-N orbitals are predicted at 314 nm or shorter wavelengths only, and they might be buried under the strong aryl absorption. Thus, it appears that the mixing of the diazirine and the aryl π-

system makes “normal” aryl diazirines absorb relatively strongly in the near UV. When

this mixing is inhibited, the diazirine no longer absorbs in this region. 95

Figure 44. HOMO and LUMO of 2- and 3-diazirine 205 and 223 .

Consistent with our hypothesis, our group has uncovered several other twisted diazirines that similarly are missing the n π* diazirine absorbance because of twisted geometries (Figure 45). Since this characteristic absorbance is generally used for spectral characterization and photoaffinity purposes, we believe these results have important, practical consequences. 96

Figure 45 . Twisted vs. normal diazirines discovered by the Sheridan group.

3.1.3 Direct observation and characterization of 3-benzothienyl(trifluoromethyl) carbene

After several trials, we found the right temperature to directly deposit the diazirine 223 into a N 2 matrix at 10 K (-10°C-0°C). The IR spectrum of the deposited

diazirine shows bands at 1622, 1526, 1464, 1434, 1365, 1303, 1265, 1234, 1207, 1190,

1169, 1157, 1145, 1130, 1057, 1039, 1030, 883, 825, 767, 762, 738, 693, and 687 cm -1.

The matrix isolated IR spectrum matched nicely with the calculated (B3LYP 6-31+G**)

IR spectrum (Figure 46). This further confirmed that the oxidized product of diaziridine

230 is indeed diazirine 223 .

1850 1650 1450 1250 1050 850 650 450

-1 Frequency (cm )

Figure 46. Top: Matrix isolated IR spectrum of 3-benzothienyl(trifluoromethyl)diazirine

(223 ) in absorbance units; bottom: B3LYP 6-31+G** predicted IR spectrum of diazirine

223 in relative intensities.

Irradiation of matrix isolated 3-benzothienyl(trifluoromethyl)diazirine (223 ) at

313 nm or 334 nm for 30 min and more caused the dissapperance of diazirine bands and appearance of new bands (1543, 1494, 1470, 1413, 1396, 1338, 1268, 1246, 1173, 1125,

1077, 1047, 923, 836, 809, 783, 736, 669, 646 cm -1) which best fit the calculated IR of 98

syn 224a (CF 3 syn to S) and anti 224b (CF 3 anti to S) (Figure 47). Syn carbene 224a was a major product.

1850 1650 1450 1250 1050 850 650 450

Frequency (cm -1)

Figure 47 . Top: B3LYP 6-31+G** predicted IR spectrum of syn carbene 224a; middle: difference IR spectra of diazirine 223 converting into carbene syn carbene 224a; bottom:

B3LYP 6-31+G** predicted IR spectrum of diazirine 223. “The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.”

B3LYP 6-31+G** predicted IR frequencies and their relative intensities for anti singlet carbene and both syn and anti triplet carbene are shown in Figure 48-50. A very intense peak calculated at 1178 cm -1 and observed at 1173 cm -1 supports prediction that observed carbene is ground state singlet. 99

500 450 400 350 300 250 200 Intensities 150 100 50 0 1850 1650 1450 1250 1050 850 650 450

Frequency (cm -1)

Figure 48 . B3LYP 6-31+G** predicted IR spectrum of anti singlet carbene 224 .

350

300

250

200

150 Intensities 100

0 1850 1650 1450 1250 1050 850 650 450

Frequency (cm -1)

Figure 49 . B3LYP 6-31+G** predicted IR spectrum of anti triplet carbene 224 . 100

300

250

200

150

Intensities 100

0 1850 1650 1450 1250 1050 850 650 450

Frequency (cm -1)

Figure 50 . B3LYP 6-31+G** predicted IR spectrum of syn triplet carbene 224 .

The UV-vis spectrum of the irradiated diazirine 223 matrix also showed distinct

differences compared to the starting material. The experimental UV-vis spectrum, with λ

max 394 nm, nicely matched the TD calculated spectrum of singlet carbenes 224 , syn

(414 nm, f=0.0482) and anti (382 nm, f=0.0711) (Figure 51). 101

1.8

1.6

1.4

1.2

1 Absorbance 0.8

0.6

0.4

0.2

-0.2 200 250 300 350 400 450 500 550 600 650 700 750 800 850 Wavelength [nm]

Figure 51 . Solid line: Matrix isolated UV-vis spectra of diazirine 223 (black) and

carbene 224 (red); solid bars: TD B3LYP 6-31+G** predicted UV-vis spectrum of

carbene 224 (red).

Irradiation of the syn carbene at 435 nm for an hour caused the disapperance of

distinct syn carbene 224a bands at 1470, 1268, 1173, 1125, 1077, 1047, 923 and 646

cm -1 while increasing the intensities of anti carbene 224b IR bands at 1465, 1336, 1229,

1166, 1082 and 918 cm -1 (Figure 52).

102

1850 1650 1450 1250 1050 850 650 450 Frequency (cm -1)

Figure 52 . Top: B3LYP predicted IR spectra of carbene 224b ; middle: difference IR

spectra showing syn carbene 224a going away and anti carbene 224b growing; bottom:

B3LYP predicted IR spectra of syn carbene 224a . “The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.”

The experimental UV-vis spectra after irradiation with 435 nm also changed as the absorption blue shifted which fits the TD B3LYP calculation of anti -carbene

224b (Figure 53). 103

2.7

2.4

2.1

1.8

1.5

1.2 Absorbance

0.9

0.6

0.3

-0.3 200 250 300 350 400 450 500 550 600 650 700 750 800 850 Wavelength [nm]

Figure 53 . Solid line: Matrix isolated UV-vis spectra of syn carbene 224a (black), and anti carbene 224b (red); solid bars: TD B3LYP 6-31+G** predicted UV-vis spectra of syn carbene 224a (black), and anti carbene 224b (red).

3.1.4 Trapping reactions of 3-benzothienyl(trifluoromethyl)carbene

Low temperature trapping of carbenes with O2 and HCl are often used to

complement the experimental and calculated results. In general triplet carbenes react with

O2 and singlet carbenes react with HCl. Addition of O 2 with triplet carbenes generates

carbonyl oxides which upon further irradiation make dioxiranes, esters, etc. Addition of

HCl with singlet carbenes generates HCl addition products, “benzylic” chlorides. The

generated trapping products are characterized by experimental IR and UV-vis spectra

and their calculated counterparts. 104

General trapping reactions in low temperature matrices are done by doping the inert gas with 0.5-5 % of trapping reagent. The precursor diazirine is sublimed onto the cold window with doped inert gas, and carbene is generated by irradiation of diazirine with an appropriate wavelength of light. Once carbene is generated, the matrix window is warmed to 30 K with a heater. Warming the matrix causes the diffusion of the trapping reagent, allowing reaction. Carbene addition products are characterized by taking experimental IR and UV-vis spectra of the products and comparing with calculated spectra.

1800 1600 1400 1200 1000 800 600 Frequency (cm -1)

Figure 54 . Top: B3LYP predicted IR spectra of benzylic chloride 231 ; middle: difference

IR spectra showing carbene 224 going away and benzylic chloride 231 forming; bottom:

B3LYP predicted IR spectra of carbene 224 . “The difference IR spectrum is shown in 105

relative absorbance units. The calculated IR spectra are each shown in relative intensities.”

In the case of 3-benzothienyl(trifluoromethyl)carbene (224 ), annealing an O2

(0.5-5%) doped matrix to 35 K did not generated the oxygen addition product. Whereas, annealing the carbene 224 in a HCl doped matrix (1-2%) generated product 231 . The new

product 231 was characterized as the HCl addition product of carbene by comparing

experimental and DFT calculated IR spectra (Figure 54). Both DFT calculations and the

trapping reactions at low temperature suggest that the carbene 224 is a ground state

singlet. B3LYP calculated energies of singlet and triplet carbenes also fit the prediction

that singlet is lower in energy than triplet. Energies of both conformers of carbene along

with other intermediates will be discussed later. Trapping reactions of carbene 224 are

summarized in Scheme 57.

106

Scheme 57 . Trapping reaction of carbene 224 in 10 K, N 2 matrix

3.1.5 Photochemical rearrangement of 3-benzothienyl(trifluoromethyl)carbene

Irradiation of carbene 224 at 404 nm produced a range of products based on the duration of irradiation. Short irradiation, from 10 min to 1 h, generated new IR bands at

1818, 1560, 1472, 1454, 1437, 1432, 1317, 1274, 1226, 1177, 1168, 1149, 1146, 1117,

1114, 1084, 776, 752, 639 and 596 cm -1. The weak band at 1818 cm -1 and bands at

1317, and 1149 cm -1 best fit the B3LYP predicted bands of bicyclic intermediate 232 .

B3LYP calculation predicts C=C stretching at 1869 cm - 1 and C-H vibration of hydrogen

of cyclopropene ring at 1309 cm -1. 107

Figure 55 . Top: B3LYP predicted IR spectra of bicyclic intermediate 232 ; middle: difference IR spectra showing carbene 224 going away and bicyclic intermediate 232 forming; bottom: B3LYP predicted IR spectra of bicyclic intermediate 232 . “The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.”

Experimental UV-vis spectra taken after irradiation at 404 nm changed significantly compared to carbene 224 . Absorption at λ max 392 nm and 380 nm decreased significantly and new absorption at 350 nm was observed. TD calculation predicts absorption of bicyclic intermediate 232 at 360 nm (f=0.0416) (Figure 56). 108

2.6

2.4

2.2

1.8

1.6

1.4

1.2 Absorbance 1

0.8

0.6

0.4

0.2

-0.2 200 250 300 350 400 450 500 550 600 650 700 750 800 850 Wavelength [nm]

Figure 56 . Solid line: Matrix isolated UV-vis spectra of bicyclic intermediate 232

(green), and carbene 224 (red and black); solid bars: TD B3LYP 6-31+G** predicted

UV-vis spectra of bicyclic intermediate 232 .

Further irradiation with 404 nm (1-17 h) caused the decrease of bicyclic

intermediate 232 and bands, 1786, 1596, 1478, 1426, 1312, 1307, 1374, 1278, 1246,

1230, 1190, 1178, 1163, 1155 and 898 cm -1 grew. The intense bands at 1278, 1155 and

bands at 898 cm -1 fit the prediction of the calculated IR spectrum of ring expanded

carbene 233 (Figure 57). 109

“The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.”

110

The UV-vis spectrum after longer irradiation with 404 nm did not change. TD calculation for ring expanded carbene 233 predicts a weak absorption at 355 nm

(f=0.0008) and strong absorption at 340 nm (f=0.052). Calculated UV-vis for both

intermediates come very close to each other and most probably overlap, which fits the

observed experimental UV-vis spectrum.

Irradiation at 366 nm for 1 h, slowly destroyed bicyclic 232 and bands at 1786,

1613, 1543, 1495, 1396, 1251, 1247, 1239, 1218, 1201, 1198 1193, 1177, 1163, 1108,

1099, 996, 807, 795, 744, 729, 668, 623 and 585 cm-1 became more intense. The

generated new set of bands closely matched the calculated IR specta of

methylenecyclopropene 235 and spirocyclic product 234 . Longer irradiation at 366 nm

converted the ring extended carbene 233 into methylenecyclopropene 235 and spiro

product 234 (Figure 58). 111

Figure 58 . Top: B3LYP predicted IR spectra of methylenecyclopropene 235 ; middle: difference IR spectra showing ring-opened carbene 233 going away and methylenecyclopropene 235 forming; bottom: B3LYP predicted IR spectra of ring- opened carbene 233 . “The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.”

112

2.2

1.8

1.6

1.4

1.2

1 Absorbance

0.8

0.6

0.4

0.2

-0.2 200 250 300 350 400 450 500 550 600 650 700 750 800 850 Wavelength [nm]

Figure 59 . Solid line: Matrix isolated UV-vis spectra of ring-opened carbene 233 (red),

and methylenecyclopropene 235 (black); solid bars: TD B3LYP 6-31+G** predicted UV-

vis spectra of ring-opened carbene 233 (red), and methylenecyclopropene 235 (black).

Even prolonged irradiation at 404 nm and 366 nm did not destroy the spirocyclic

product 234. But, irradiation at 313 nm caused the dissapearance of spiro product 234

and the methylene cyclopropene 235 grew.

UV-vis spectra before and after irradiation at 313 nm did not show any noticeable change. TD B3LYP calculation shows UV-vis absorption at 336 nm(f=0.0174) for the spirocyclic intermediate 234 . Since all three intermediates, bicyclic 232 , ring-open 233

and spiro 234 have absorptions around 330-350 nm, the broad absorption observed in the

experimental UV-vis spectra might be an overlap of all three intermediates (Figure 60). 113

2.4 F3C

2.2

2 S

1.8 CF3

1.6 S 1.4 CF3 1.2 Absorbance 1 S 0.8

0.6

0.4

0.2

-0.2 200 250 300 350 400 450 500 550 600 650 700 750 800 850 Wavelength [nm]

Figure 60 . Solid line: Matrix isolated UV-vis spectra of intermediates 232, 233 and 234 ;

solid bars: TD B3LYP 6-31+G** predicted UV-vis spectra of intermediates 232 (black),

233 (red) and 234 (blue).

Irradiation of methylene cyclopropene 235 at 547 nm slowly caused it to

disappear, and produced ring extended carbene 233 (Figure 61), bicyclic intermediate

232 and spirocyle 234 . These photochemical transformation are summarized in Scheme

58. 114

1850 1650 1450 1250 1050 850 650 450

Frequency (cm -1)

Figure 61. Top: B3LYP predicted IR spectra of ring-opened carbene 233; middle:

difference IR spectra showing methylenecyclopropene 235 going away and ring-opened

carbene 233 forming; bottom: B3LYP predicted IR spectra of methylenecyclopropene

235 . “The difference IR spectrum is shown in relative absorbance units. The calculated

IR spectra are each shown in relative intensities.”

115

Scheme 58 . Photochemical rearrangement of carbene 224 at 10 K, N 2 matrix

3.1.6 Deuterium labeling

The complexity of vibrational spectra and the plethora of intermediates uncovered inspired us to think about deuterium labeling. The deuterium shifts in the IR spectra may be significant in these intermediates compared to parent molecules.

We started with deuterating benzothiophene with commercially available D 6 DMSO and

sodium hydride. Taking advantage of the acidity of the 3-H of the thiophene ring in

benzothiophene, we were able to achieve 90 %+ deuteration result by 1H NMR. 116

Compared to parent precursors, however, the deuterated precursors were very messy and extremely difficult to purify for unknown reasons. We were never able to get clean single precursors of deuterated products beside diazirine 223i .

We were able to deposit the deuterated diazirine 223i onto cold window using

similar condition as proteo diazirine 223 . The experimental IR spectrum of deuterated

diazirine was clean and nicely matched the calculated IR spectrum with distinct

deuterium shifts compared to proteo diazirine (Figure 62). The UV-vis spectrum is

similar to proteo diazirine 223 .

1.1

0.9

0.8

0.7

0.6

Absorbance 0.5

0.4

0.3

0.2

0.1

0 1750 1650 1550 1450 1350 1250 1150 1050 950 850 750 650 550 450 Wavenumbers [1/cm]

Figure 62. Matrix isolated IR spectrum of deuterated 3-diazirine (223i ) in 10 K, N 2

matrix.

117

Deuterium labeling confirmed our diazirine (Figure 62), carbene (Figure 63) and its rearrangement products. But, we were not able to get any better deuterated IR spectra than proteo products, especially of bicyclic intermediate 232i and ring expanded carbene

233i. The experimental deuterium shifts were consistent with the calculated results which further confirm our intermediate characterizations. In the case of methylene cyclopropene

235 (1785 to 1747 cm -1) and spiro product 234 (1776 to 1724 cm -1) we saw clear

evidence of deuterium shifts in experimental IR spectra, however (Figure 64-65).

1800 1600 1400 1200 1000 800 600 Frequency (cm -1)

Figure 63. Top: B3LYP 6-31+G** predicted IR spectrum of deuterated carbene 224i;

middle: difference IR spectra of deuterated diazirine 223i converting into carbene 224i; bottom: B3LYP 6-31+G** predicted IR spectrum of diazirine 223i . “The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.” 118

Figure 64 . Top: B3LYP predicted IR spectra of deuterated methylenecyclopropene 235i; middle: difference IR spectra showing bicyclic product 232i going away and methylenecyclopropene 235i forming; bottom: B3LYP predicted IR spectra of deuterated bicyclic product 232i . “The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.”

119

Figure 65 . Top: B3LYP predicted IR spectra of deuterated methylenecyclopropene 235i; middle: difference IR spectra showing deuterated spiro product 234i going away and methylenecyclopropene 235i forming; bottom: B3LYP predicted IR spectra of deuterated spiro product 234i. “The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.”

3.1.7 Possible mechanisms

Possible mechanisms for formation of ring expanded carbene 233 and spiro product 234 and their rearrangment into methylene cyclopropene 235 are shown in

Scheme 59. 120

Scheme 59 . Possible mechanism of rearrangement of carbene 224 into 232, 233, 234,

and 235.

3.1.8 Study of C 10 H5F3S potential energy surface

Calculations show that anti singlet carbene 224 is 2 kcal/mol lower in energy than

triplet. B3LYP calculations overestimate triplet stabilities by approximately 2

122 kcal/mol. So, just like the 2-isomer, CF 3 carbene 224 is also a ground state singlet. In

the case of carbene 233 , B3LYP calculation predicts singlet 233 is 6.0 kcal/mol lower

than triplet 233 . Carbene 233 is a ground state singlet due to aromatic stabilization.

A comparative table of energies of both 2- and 3-benzothienylcarbenes and their rearranged products is shown in Figure 66. 121

Figure 66 . B3LYP predicted relative energies of 2- and 3-carbenes, 206 and 224 and

their rearranged products. 122

In summary, we were able to spectroscopically observe and characterize carbene

224 in low temperature N 2 matrices. Similar to 2-benzothienylcarbene 206, 3-benzo-

thienylcarbene 224 is also a ground state singlet . Futhermore, we were able to observe

and characterized several new elusive intermediates such as 232 , 233 and 234 via IR and

UV-vis spectra. In addition, we also discovered the UV-vis transparent twisted diazirine

223 .

3.2 N-Methyl-2-indolyl(trifluoromethyl)carbene

Although carbenes attached to 5-membered heterocycles containing sulfur

and oxygen have been explored by the Sheridan group and others, studies of carbenes

attached to 5-membered heterocycles containing nitrogen are few. Shevlin’s group 123

reported that addition of atomic carbon to pyrrole makes a species best described as a

dehydropyridinium ylide rather than a cumulene, based on calculation. Trapping with

methanolic HCl with the cold condensates of N-methyl pyrrole and atomic carbon

generated the N-methylpyridium ion. As mentioned before, the Sheridan group has

observed several highly strained cumulenes such as 132 , 188 , 194 , 199 , 204 and 208

(Figure 67 ) generated from rearrangement of heteroarylcarbenes. Carbenes attached to

indole and pyrrole could similarly lead to strained cumulenes. In the cumulenes

generated from indole and pyrrole, however, nitrogen is in a different position than in

199 and 204 .

Contrary to benzoxazole and benzothiazole 5-membered rings which are electron

deficient, the indole 5-membered ring is electron rich. More importantly, compared, to 123

sulfur and oxygen, nitrogen containing cumulenes might have more aromatic and zwitterionic character. Spectroscopic characterization of these species has not been successful yet, not only because of their reactivity, but also difficulty in synthesizing precursor diazirines. Although our group has synthesized and studied halo diazirines attached to furans and thiophenes, and have developed methods to handle these highly reactive diazirines, we have not been successful in synthesizing halo diazirines attached to indole or pyrrole. Motivated by the successful synthesis of trifluoromethyl diazirines attached to benzofuran and benzothiophene, and observation and characterization of the carbenes and their rearranged products, we sought to explore trifluoromethyl diazirines attached to indole and pyrrole. We predicted, compared to cumulenes with sulfur, 132 ,

194 and 208a, nitrogen should make these planar and aromatic, 236b rather than 236a for

example (Figure 68).

Figure 67. Cumulenes characterized by the Sheridan group, spectroscopically in low

temperature matrices.

124

Figure 68 . Predicted nitrogen containing cumulene.

Since carbenes attached to the 2-position of 5-membered nitrogen containing

heterocycles have not been characterized spectroscopically, observation and

characterization of 2-indolyl carbene would provide valuable information about the

reactivity and electronics of these species. Also, indole(trifluoromethyl)diazirine might

open the way for new photoaffinity labeling agents.

3.2.1 Synthesis of 2-N-methyl-indolyl(trifluoromethyl)diazirine

To avoid the tosylation/mesylation of the indole nitrogen (will be discussed in 3- indole case), we decided to protect the indole nitrogen with a relatively small methyl group, hoping that the reactivity and volatility of diazirine wouldn’t be affected to a great extent.

Indole ( 237 ) was N-methylated by dissolving in acetone and treating with

potassium hydroxide (KOH) and methyl iodide (MeI). 124,125 After workup, the product

was purified via distillation under reduced pressure.

In the case of benzothiophene, both 2- and 3- isomers of (trifluoromethyl) ketone

were prepared by treating with butyl lithium reagent and trifluoroacetic anhydride in the

presence of copper reagent(CuBr(CH 3)2S). But, in the case of indole, since the 3- position 125

is more electron-rich than 2-, and the 3-position can undergo electrophilic aromatic substitution easily, a different approach to prepare the 2- ketone was required. Several studies describe lithiation of the 2-position of indole since the 2-H is comparatively more acidic than the 3-hydrogen. 124,126

H 3 2 H N H 237

Figure 69. 2- and 3- position hydrogen in an indole (237 ).

N-Methyl-indole ( 238 ) was lithiated at the 2-position following literature procedures by treating with t-BuLi at -60°C. 124 The generated lithium reagent was treated

with piperidine(CF 3)amide 239 to generate the N-methy- 2-indolyl(CF 3) ketone, 240 .

After workup, the product was recrystallized in ethanol. 1H NMR, 13 C, 19 F spectra were taken and compared with the 3-ketone (see later section for synthesis) to make sure that the obtained ketone was indeed the pure 2-isomer, 240 . Proton NMR spectra of the two isomers of ketone are clearly distinct. 126

Figure 70. 1H NMR spectra of 2- and 3-indolyl(trifluoromethyl)ketone.

N-Methyl-2-indolyl(trifluoromethyl)oxime ( 241) was prepared following the hydroxylamine hydrochloride and pyridine method. But, excess hydroxylamine hydrochloride reagent was required for conversion of ketone to oxime. Pure ketone 240 was dissolved in ethanol and refluxed 66 h in the presence of hydroxylamine hydrochloride and pyridine. After workup, N-methyl-2-indolyl(trifluoromethyl)oxime

(241) was obtained which was used to prepare mesyl oxime 242 . 127

The oxime 241 was dissolved in dry THF and treated with mesyl chloride (MsCl) and

triethylamine(Et 3N). After evaporation of THF under reduced pressure, and after work-

up, obtained solid product 242 was recrystallized in ether and hexane.

The diaziridine 243 was prepared by treating the mesyl oxime 242 with liquid

ammonia. After work up with water and purification via silica gel column, clean yellow

colored diaziridine 243 was recovered. The diaziridine NH peaks appeared at 2.5 and 2.9

ppm in the 1H NMR.

Oxidation of the diaziridine 243 to make diazirine 244 was done using iodine and

TEA keeping the reaction mixture between -50 °C to 0 °C. Reaction conditions were

optimized and we found that oxidation at 0 °C works fine provided that the reaction was

worked up with cold sodium hydroxide solution within 30 min. The diazirine 244 was

purified via vacuum at distillation -20 °C. But, even after distillation, the NMR showed

presence of Et 3N which was not removed as the diazirine decomposed under acidic work- up. Diazirine 244 was purified via sublimation onto the cold matrix window. The complete synthetic procedure is shown in Scheme 60.

128

Scheme 60 . Synthesis of N-methyl-2-indolyl(trifluoromethyl)diazirine (244)

3.2.2 Direct observation and characterization of N-methyl-2-indolyl(trifluoromethyl)carbene

N-methyl-2-indolyl( trifluoromethyl )diazirine (244 ) was sublimed onto cold window

(21 K) from a bath temperature of -10 °C along with 50-75 torr of nitrogen. As with other

hindered aryldiazirines, the experimental UV-vis spectrum of diazirine 244 did not show

characteristic n π* absorption.

129

5.1

4.8

4.5

4.2

3.9

3.6

3.3

3 Absorbance

2.7

2.4

2.1

1.8

1.5

1.2 200 250 300 350 400 450 500 550 600 650 700 750 800 850 Wavelength [nm]

Figure71 . Solid line: Matrix isolated UV-vis spectrum of N-methyl-2-indolyl(trifluoromethyl)diazirine (244 ); solid bars: TD B3LYP 6-31+G** predicted UV-vis spectrum of diazirine 244 .

TD B3LYP calculation predicts only weak absorption at 495 nm (f=0.0055). The calculations show that the trifluoromethyl group of the diazirine 244 is turned 90° out of

plane compared to normal aryldiazirines. This geometric difference is likely due to the

steric hindrance between methyl group attached to N and the diazirine.

130

Experimental IR spectra show bands at 1634, 1618, 1601, 1549, 1474, 1466,

1433, 1401, 1387, 1365, 1353, 1328, 1301, 1294, 1270, 1272, 1240, 1223, 1202, 1181,

1169, 1166, 1154, 1147, 1133, 1104, 1086, 1077, 1064, 1042, 955, 926 and 903 cm -1.

B3LYP predicted IR bands fit the experimental spectrum (Figure 72).

1800 1600 1400 1200 1000 800 600 400

1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700 600 500 400 Frequency (cm -1)

Figure 72 . Top: B3LYP predicted IR spectrum of diazirine 244 in relative intensities;

bottom: matrix isolated IR spectrum of diazirine 244 in absorbance units.

The diazirine 244 was found to be photoreactive at 482, 313 and 265 nm.

Irradiation of diazirine at 482 nm for 30+min destroyed diazirine IR bands and generated 131

new IR bands at 2218-2240, 2105, 1635, 1626, 1555, 1464, 1422, 1379, 1336, 1290,

1245, 1229, 1216, 1186, 1179, 1161, 1147, 1135, 1116, 1081, 1072, 1059, 1044, 985 and

924 cm -1. Except, 2218, 2105 and 1290 cm -1, the other bands nicely fit the B3LYP calculated IR bands of mostly syn (methyl and CF 3) singlet carbene 245a (Figure 73).

B3LYP predicted IR spectra of both syn and anti carbenes are shown in Figure 74.

Figure 73 . Top: B3LYP predicted IR spectra of syn carbene 245a; middle: difference IR spectra showing diazirine 244 going away and syn carbene 245a forming; bottom:

B3LYP predicted IR spectra of diazirine 244 . “The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.” 132

600

500

400

300

Intensities 200

100

0 1800 1600 1400 1200 1000 800 600 Frequency (cm -1)

Figure 74 . B3LYP predicted IR spectra of syn (red) and anti (black) carbene 245a and

245b .

The UV-vis spectra also changed significantly after irradiation at 482, 313 or 265

nm. TD B3LYP calculation for singlet syn (methyl and CF 3) carbene 245a predicts absorption at 988 nm (f=0.0007), 449 nm (f=0.0331) and 312 nm (f=0.5118) and for singlet anti (methyl and CF 3) carbene 245b at 865 nm (f=0.0012), 449 nm (f=0.0349), and 310 nm (f=0.5083) (Figure 75). We usually don’t see any absorption above 800 nm in our UV-vis spectrometer. We do observe a broad absorbance around 460 nm and an intense UV-vis absorption around 359 nm. B3LYP calculated energies also predict that singlet carbene is lower in energy than triplet (see below, DFT section). 133

5.2

4.8

4.4

3.6

3.2 Absorbance 2.8

2.4

1.6

1.2

0.8 200 250 300 350 400 450 500 550 600 650 700 750 800 850 Wavelength [nm]

Figure 75 . Solid line: Matrix isolated UV-vis spectrum of N-methyl-2-indolyl(trifluoromethyl)carbene (245); solid bars: TD B3LYP 6-31+G** predicted UV-vis spectrum of carbene 245

3.2.3 Photochemical rearrangement of N-methyl-2-indolyl(trifluoromethyl)carbene

Irradiation of the carbene 245 at 349 nm destroyed carbene bands and generated

intense bands at 1288-90 and 1143-1155 cm -1. These IR bands were generated along with

carbene initially, but they became more intense. Also bands at 2218-2240, 1585, 1073

cm -1 grew. The B3LYP predicted IR spectrum of ring opened quinoimine 246 nicely fits

the experimental IR spectrum (Figure 76). The UV-vis spectra do not change much, but

still a slight difference can be seen if both carbene 245 and quinoimine 246 spectra are overlayed (Figure 77). TD B3LYP calculations predict absorption for anti (methyl and 134

CF 3) quinomethide at 456 nm (f=0.1707) and 303 nm (f=0.0897) and for syn (methyl and

CF 3) quinoimine at 437 nm (f= 0.0716), 418 nm (f=0.0598) and 293 (f=0.1022). Thus the

UV-vis spectra also fit predictions for ring-open product 246 .

Figure 76 . Top: B3LYP predicted IR spectra of quinoimine 246 ; middle: difference IR spectra showing syn carbene 245a going away and quinoimine 246 forming; bottom:

B3LYP predicted IR spectra of syn carbene 245a. “The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.”

135

Irradiation of the quinoimine 246 at 265 nm, 366 nm, 375 nm or 404 nm destroyed the quinoimine IR bands and produced the carbene 245 IR bands (Figure 78), and this process was reversible.

However, irradiation of quinomethide 246 at 523 nm appeared to photochemically trigger syn -anti isomerization of quinoimine, based on shifts in the IR spectra (Figure

79).

5.6

5.2

4.8

4.4

3.6 Absorbance 3.2

2.8

2.4

1.6

1.2 200 250 300 350 400 450 500 550 600 650 700 750 800 Wavelength [nm]

Figure 77. Solid line: Matrix isolated UV-vis spectra of carbene 245 (red) and quinoimine 246 (black); solid bars: TD B3LYP 6-31+G** predicted UV-vis spectra of quinoimine 246 .

136

Figure 78 . Top: B3LYP predicted IR spectra of syn carbene 245a; middle: difference IR spectra showing quinoimine 246 going away and syn carbene 245a forming; bottom:

B3LYP predicted IR spectra of quinoimine 246 . “The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.”

137

Figure 79 . Top: B3LYP predicted IR spectra of syn quinoimine 246b ; middle: difference

IR spectra showing anti quinoimine 246a going away and syn quinoimine 246b forming; bottom: B3LYP predicted IR spectra of anti quinoimine 246a . “The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.”

The overall photochemical rearrangements in low temperature matrices are shown in

Scheme 61. 138

Scheme 61 . Matrix isolation study of the diazirine 244

3.2.4 Study of C 11 H8F3N potential energy surface

Figure 80 . B3LYP predicted energies of carbene 245 and its rearranged products. 139

Anti carbene 245b is lower in energy than syn carbene 245a , and steric hindrance between the methyl and trifluoromethyl groups might be a reason for this. The same applies for the ring opened quinoimine 246 where anti conformer 246a is lower in energy

than syn conformer 246b . As expected, both ring expanded aromatic zwitterions 236b and 247 are lower in energy than carbene.

CF3 + N N CF3 CH3 CH3 245b 245a

CF3

CF N N 3 248 CH3 246 CH3

CF3

N N CF3 CH3 CH3 247 236b Figure 81 . Possible mechanism for formation of zwitterions 236b and 247 from carbene

245 .

We envision two possible ways that carbene 245 might cyclize and form zwitterions 247 and 236b . But, experimentally we were not able to find a suitabale

wavelength to produced any of these two species in low temperature matrices. B3LYP 140

predicted calculated IR and UV-vis spectra of both 247 and 236b are close to the calculated carbene spectra which are shown below (Figure 82-85).

300

250

200

150

Intensities 100

0 1800 1600 1400 1200 1000 800 600 Frequency (cm -1)

Figure 82 . B3LYP predicted IR spectrum of 236b .

0.1 0.09 0.08 0.07 0.06 0.05 0.04 Absorbance 0.03 0.02 0.01 0 200 300 400 500 600 Wavelength (nm)

Figure 83 . TD B3LYP predicted UV-vis spectrum of 236b .

141

200 180 160 140 120 100 80 Intensities 60 40 20 0 1800 1600 1400 1200 1000 800 600

Frequency (cm -1)

Figure 84 . B3LYP predicted IR spectrum of 247 .

0.18 0.16 0.14 0.12 0.1 0.08 0.06 Absorbance 0.04 0.02 0 180 280 380 480 580 Wavelength (nm)

Figure 85 . TD B3LYP predicted UV-vis spectrum of 247 .

142

The possiblity of zwitterions cannot be ruled out considering both carbene 245 and quinoimine 246 has strong IR vibrations where 236b and 247 IR vibrations are

predicted. Also ring expanded carbenes, 236b and 247 vibrations are relatively weaker

than carbene 245 and quinoimine 246 .

Thus, in the case of the N-methyl-2-(trifluoromethyl) indole system, we were able

to synthesize the precursor diazirine 244 and observed and characterized 2-N-methyl( trifluoromethyl)indolylcarbene 245 in low temperature nitrogen matrices. The carbene ring opened into quinoimine 246 , and this process was photochemically reversible. Also, quinoimine 246 photochemically isomerizes into E-Z conformer. However, the spectra do

not allow us to say for certain whether or not zwitterionic products 247 and 236b are also formed.

3.3 N-methylated-3-indolyl(trifluoromethyl)carbene

As described above, studies of carbenes attached to the 3-position of 5- membered-heteroaryl rings are relatively few. McMahon’s 3-thienyl carbene is the latest study reported in this series. 71 After successful observation and characterization of 3- benzothienyl(CF 3)carbene 224 , here we report the direct observation and characterization of a carbene attached to the 3-position of N-methyl- indole.

143

3.3.1 Synthesis of N-methyl- 3-indolyl(trifluoromethyl)diazirine

Compared to 2-indolyl(trifluoromethyl)ketone (249 ), synthesis of the 3-indolyl-

(trifluoromethyl)ketone 250 is relatively easy. Since the 3-position of indole is more

electron rich than the 2-position, the 3-position easily undergoes electrophilic aromatic

substitution. 3-indolyl(trifluoromethyl)ketone ( 250 ) was synthesized following known procedures. 126-128 Indole ( 237) was dissolved in dry ether and treated with trifluoroacetic anhydride (TFAA) dropwise at -10°C. After workup with water and recrystallization in ethanol, pure ketone 250 was obtained in more than 90% yield. Characterization of the ketone 250 was confirmed by 1H, 13 C and 2D NMR spectroscopy. Similar to the benzothiophene case, synthesis and characterization of the correct regioisomer is important, and we made sure we had the 3-indolyl(trifluoromethyl)ketone by the above mentioned characterization techniques. Although the 3-indolyl(trifluoromethyl) ketone

(250 ) is known, we could not find spectroscopic characterization details in the literature.

Figure 86 . 2- and 3-indolyl(trifluoromethyl)ketone 249 and 250.

3-Indolyl(trifluoromethyl)oxime ( 251 ) was prepared following the hydroxylamine hydrochloride and pyridine method similar to 241 . The reaction mixture was refluxed for

24 h to give the desired product. The oxime was used to prepare tosyl oxime using p- 144

TsCl as described in the 3-benzothiophene case. After work-up, the 1H NMR spectrum

showed an extra p-tosyl group. The 13 C NMR spectrum also showed extra carbons

consistent with an extra tosyl group. ESI+ mass spectra showed a parent ion peak of m/z

= 532. The obtained tosylated product was thus characterized to be N-tosyl-3-indolyl

(trifluoromethyl)tosyloxime 253 not 252 .

Scheme 62 . Synthesis of 3-indolyl(trifluoromethyl)ketone 250 and oxime 251

Putting a tosyl group as N protection on the indole would in fact increase the stability of the diazirine but decrease its volatility and reactivity. Since the indole nitrogen was susceptible for substitution, we addressed this issue without compromising the reactivity of carbene and volatility of diazirine. Hence, we used methyl group as a 145

protecting group on the nitrogen atom. Volatility is important for subliming diazirine into a matrix in particular.

The 3-indolyl(trifluoromethyl)ketone ( 250 ) was N-methylated by treatment with

potassium carbonate and methyl iodide. 125 The reaction was monitored via 1H NMR and

showed the disappearance of the N-H peak and appearance of a methyl peak. Attempts to

prepare N-methyl-3- ketone 254 by first methylating the indole and doing electrophilic

aromatic substitution was not efficient.

The hydroxylamine hydrochloride and pyridine method was used to prepare 3-N-

methylindolyl(trifluoromethyl)oxime ( 255 ). But, similar to the 2-indole case, excess hydroxylamine reagent was required for conversion of ketone to oxime. The reaction mixture was refluxed for 50 h to get the desired product.

3-Oxime 255 was converted into 3- N-methylindolyl(trifluoromethyl)tosyloxime

(256 ) by treating with p-TsCl, triethylamine and a catalytic amount of dimethylaminopyridine. But, tosyloxime 256 did not generate clean diaziridine in either low temperature ammonia reaction or under pressure. One probable reason might be steric hindrance to nucleophilic attack, although the electron-rich indole ring may also make tosyloxime less reactive. 146

Figure 87 . Resonance structure of tosyloxime 256 .

So, compared to 256 a less bulky mesyloxime 257 was prepared from the oxime

255 . The oxime 255 was dissolved in dry tetrahydrofuran (THF) and treated with

triethylamine (TEA) and mesylchloride at -35 °C. After workup, the product was

characterized by 1 H NMR spectroscopy, which showed the disappearance of the OH peak

and appearance of the methyl peak of the mesyl group. The mesyl oxime 257 was dissolved in dichloromethane and treated with liquid ammonia at -78 °C for 36 h. After evaporation of excess ammonia at room temperature and work-up with water, diaziridine

258 was recovered.

The indole ring is susceptible to oxidation reactions. After several trials, a workable method to oxidize diaziridine 258 to diazirine 259 was found with iodine and

Et 3N and keeping the reaction mixture cold (-25 °C to 0 °C) with overall reaction time

between 2-20 min, in the dark. After work up with ice chilled sodium hydroxide solution

and cold dichloromethane, diazirine 259 was obtained. Acidic work-up destroyed the diazirine, so complete removal of triethylamine was not possible. But, diazirine 259 was 147

purified via cold distillation into a -20 °C cold trap and directly sublimed onto the cold matrix window keeping in the dark.

Scheme 63 . Synthesis of 3-N-methylindolyl(trifluoromethyl)diazirine (259)

3.3.2 Direct observation and characterization of N-Methyl-3-indolyl(CF 3)carbene

Diazirine 259 was sublimed onto the cold CsI window (21K) from various

temperature ranges from -10 °C to room temperature with 60-120 torr of nitrogen.

Contrary to the 3-benzothienyl(trifluoromethyl) case where n π* absorption was not observed, in the 3-N-methyl- indole case a weak nπ* absorption was observed in the

experimental UV-vis spectra. The UV-vis spectrum of diazirine 259 at 10 K in N 2 matrices showed (weak) absorption at 446 nm, 419 nm, 395 nm and 373 nm (Figure 88).

Weaker absorption at 480 nm and 314 nm was also observed. TD B3LYP calculation predicts n π* absorption at 454 nm (f=0.0086), 372 nm (f=0.0013), and 314 nm (0.0013) 148

which approximately fits the experimental UV-vis spectra. It is interesting that the 3-N- methyl(trifluoromethyl)diazirine (259 ) absorption strength (f=0.009) is only slightly

stronger than 3-benzothienyl(CF 3)diazirine ( 223 ) absorption strength (f=0.007) in TD calculation. The splitting pattern of diazirine absorption looks similar to other diazirines but is very weak.

2.3

2.2

2.1

1.9

1.8 Absorbance 1.7

1.6

1.5

1.4

1.3 300 320 340 360 380 400 420 440 460 480 500 520 540 560 Wavelength [nm]

Figure 88 . Matrix isolated UV-vis of diazirine 259 .

The experimental IR spectrum of 3-N-methyl(trifluoromethyl)diazirine 259 at

10 K in N 2 matrices showed bands at 1600, 1555, 1483, 1471, 1455, 1430, 1409, 1400,

1381, 1355, 1336, 1307, 1301, 1259, 1237, 1202, 1191, 1159, 1145, 1070, 1069, 1064,

1042, 1029, 880, 769, 743 and 710 cm -1. The B3LYP predicted IR spectrum of diazirine

259 nicely fit the experimental IR spectrum. 149

Irradiation of the diazirine 259 with 435 nm light at 10 K in N 2 matrices

destroyed the diazirine IR bands and generated new IR bands at 2089, 1531, 1474,

1462, 1449, 1440, 1416, 1410, 1390, 1361, 1332, 1326, 1294, 1249, 1227, 1208, 1198,

1182, 1176, 1156, 1134, 1127, 1119, 1112, 1103, 1092, 1087, 1079, 1051, 1041, 1015,

1012, 894, 845, 840, 756, 723, and 464 cm -1. The band at 2089 is consistent with a diazo

band. Other bands fit the predicted IR spectra of B3LYP calculation for singlet syn 260a

(CF 3 syn to nitrogen) carbene with traces of singlet anti carbene 260b (Figure 89). DFT calculation also predict that singlet is lower in energy than triplet, as will be described below.

The experimental UV-vis spectrum also changed after irradiation with 435 nm light and new absorption around 340 nm was observed (Figure 90). This new absorption is consistent with TD B3LYP calculation which predicts absorption at 343 nm (f=0.0583) for syn carbene 260a and 337 nm (f=0.0011) for anti carbene 260b . In both syn and anti carbenes, calculations predict weak long wavelength absorptions at 780 nm (f=0.0016) for syn carbene 260a and at 766(f=0.0010) for anti carbene 260b , but these were not

observed in experimental UV-vis spectra. 150

1800 1600 1400 1200 1000 800 600 Frequency (cm -1)

Figure 89 . Top: B3LYP predicted IR spectra of syn carbene 260a ; middle: difference IR spectra showing diazirine 259 going away and carbene 260 forming; bottom: B3LYP predicted IR spectra of diazirine 259 . “The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.”

3.3.3 Trapping reactions of N-Methyl-3-indolyl(CF 3)carbene

As expected, the N-methyl-3-indolyl(trifluoromethyl)carbene ( 260 ) did not react with oxygen, whereas preliminary experiments indicated reaction with HCl generating addition product 261 (Scheme 64). 151

5.1

4.8

4.5

4.2

3.9

3.6

3.3

3 Absorbance

2.7

2.4

2.1

1.8

1.5

1.2 200 250 300 350 400 450 500 550 600 650 700 750 800 850 Wavelength [nm]

Figure 90 . Solid line: Matrix isolated UV-vis spectra of diazirine 259 (red) and carbene

260 (black); solid bars: TD B3LYP 6-31+G** predicted UV-vis spectra of diazirine 259

(red) and carbene 260 (black).

Scheme 64 . Trapping reaction of carbene 260 with HCl and O 2 in nitrogen matrices

3.3.4 Photochemical rearrangement of N-methyl-3-indolyl(trifluoromethyl)carbene

Irradiation with 265 nm light destroyed the syn carbene 260a and generated new

IR bands at 1547, 1528, 1473, 1465, 1458, 1416, 1249, 1245, 1178, 1135, 1122, 1104, 152

1101, 1093, 1084, 1073, 1054, 1014, and 860 cm -1. The new bands fit B3LYP predicted

IR spectra of anti -carbene 260b . The experimental UV-vis spectrum does not change. As discussed before, calculation predicts absorption for both syn and anti carbene very close to each other, 343 nm and 337 nm. In the mean time a band at 2089 cm -1 slowly went and a new band at 2016 cm -1 grew (Figure 91). We cannot so far definitely identify what products these bands correspond to.

Irradiation at 297-313 nm for 13-47 h slowly destroyed carbene and generated

IR bands at 1777, 1683, 1613, 1554, 1498, 1465, 1452, 1445, 1385, 1316, 1307, 1290,

1269, 1244, 1216, 1199, 1178, 1173, 1140, 1130, 1096, 1076, 916 , 905, 798 and 744 cm -1. The complex nature of the IR spectra indicates that the matrices consist of several

products. Comparing the experimental IR spectra with calculated IR spectra of possible

intermediates indicates that the products formed might be the methylenecyclopropene

265 and ring expanded carbene 264 , but not definitively.

IR Bands at 1777, 1613, 1498, 1465 cm -1 are consistent with methylenecyclopropene 265 calculated IR spectra (Figure 92). A similar pattern was observed in 3-benzothiophene methylenecyclopropene 235 . Bands at 905 and 916 cm -1 could be due to ring expanded carbene 264 . 153

Figure 91 . Difference IR spectra showing 2089 cm -1 going away and 2016 cm -1 growing shown in relative absorbance units. 154

1900 1700 1500 1300 1100 900 700 500

Frequency (cm -1)

Figure 92 . B3LYP predicted IR spectra of syn (red) and anti (black) conformer of methylenecyclopropene in relative intensities.

Overall, preliminary matrix isolation observations of diazirine 259 in low

temperature N2 matrices are shown in Scheme 65. Based on similar systems, the N-

methyl-3-indolylcarbene might rearrange into the following products as shown in Scheme

65.

155

Scheme 65 . Matrix isolation study of diazirine 259, carbene 260 and possible rearrangement products

3.3.5 Study of C 11 H8F3N potential energy surface

B3LYP calculated energies (Figure 93) show that singlet carbene 260a is

8kcal/mol lower than triplet indicating strong electron donation of indole (Figure 94).

Also, contrary to 3-benzothienyl bicyclic intermediate 232 , which is lower in energy than

carbene 224 , in the indole case, the bicyclic intermediate 262 is 15.0 kcal/mol higher than carbene 260 . Compared to 3-benzothienyl, both spiro product, and methyelene- cyclopropene are higher in energy

156

Figure 93 . B3LYP predicted energies of carbene 260 and possible rearrangement products.

Figure 94 . Resonance structure of carbene 260 . 157

Comparative energies of 3-benzothienyl, and 3-N-methy- indole carbene rearrangements products are shown in Figure 95.

Figure 95 . B3LYP predicted energies of carbenes 224 and 260 and their possible rearrangement products.

In summary, we have synthesized N-methylated-3-indolyl(trifluoromethyl)- diazirine ( 259 ) and generated N-methylated-3-indolyl(CF 3)carbene ( 260 ) in low

temperature matrices. We have also shown that carbene rearranges into new products. 158

These results are preliminary and tentative, and further work will be necessary to identify the product and explore the photochemistry of this system in more detail.

3.4. Benzothiazolyl(trifluoromethyl)carbene

Successful observation and characterization of highly strained cumulenes such as didehydrobenzopyran 188 , didehydrobenzothiopyran 194 and 208a, and didehydrobenzoxazine 199a have raised discussion not only about distortions from their geometries, but also the amounts of allenic, diradical and zwitterion character in these strained systems. Observations from the Sheridan group indicate that compared to oxygen, sulfur analogues have more allenic character. Published and unpublished results from the Sheridan group show that sulfur allows more twisted geometries in cyclic

108 cumulenes compared to oxygen analogues. Both chloro and CF 3 didehydro-

benzothiopyran 194 and 208a have more allenic character than didehydrobenzopyran

188 . Interestingly, didehydrobenzoxazine 199a shows considerable diradical character.

Since nitrogen, oxygen and sulfur all have different properties; didehydrobenzothiazine

should have different characteristics than didehydrobenzoxazine. The sulfur analogue of

benzoxazine can be prepared from benzothiazolyl carbene. Unpublished results from

Nikitina and Sheridan show that benzothiazolylchlorocarbene 203 rearranges into the corresponding ketenimine 204 which has more cumulenic character compared to didehydrobenzoxazine. 159

3.4.1 Synthesis and matrix isolation study of benzothiazolylchlorodiazirine(A.

Nikitina, unpublished results)

Nikitina and Sheridan synthesized benzothiazolylchlorodiazirine (202 ) starting

from the corresponding 1, 3-benzothiazole-2-carbonitrile (266 ) in two steps using

Garigipati’s reaction and Graham procedures . 129

Scheme 66 . Synthesis of diazirine 202

The UV-vis of the chloro diazirine 202 showed n π* absorption at 389, 370, 352

and 335 nm. They found that irradiation of the diazirine 202 at 334 nm and 366 nm in a

N2 matrix at 8-10 K generated singlet carbene 203 , mostly syn isomer. An additional product was also observed along with carbene 203 . Experimental UV-vis spectra of carbene showed broad absorption at 370 and 440 nm. Complete disappearance of diazirine 202 was not achieved even at prolonged irradiation at 334 nm. A possible

explanation is that the newly formed carbene blocks the UV light from the rest of the

molecules of diazirine which reside in the deepest layers in the matrix. 160

N ..

S Cl

N N N N hv .. λ = 334 nm S Cl S Cl

2200 2000 1800 1600 1400 1200 1000 800 600

N N N

S Cl

Frequency (cm -1)

Figure 96 . Top: B3LYP predicted IR spectra of carbene 203 ; middle: difference IR

spectra showing diazirine 202 going away and carbene 203 forming; bottom: B3LYP predicted IR spectra of diazirine 202 (A. Nikitina, unpublished results). “The difference

IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.”

Irradiation of the diazirine 202 at 334 nm for a prolonged period or at 366 nm,

generated chloro ketenimine 204 (Figure 97). The experimental UV-vis spectrum of 161

chloro ketenimine 204 showed broad absorption around 480 nm. Both experimental IR and UV-vis spectra fit B3LYP predicted calculated IR and UV-vis spectra of 204 (Figure

98). Though ketenimine 204 is proposed to form via a quinoimine intermediate, 268 ,

evidence of the quinoimine intermediate was not observed in the chlorocarbene

rearrangement. The overall reaction of diazirine 202 is summarized in Scheme 67.

S Cl

N N hv .. λ = 366 nm S Cl S Cl

N ..

S Cl

2200 2000 1800 1600 1400 1200 1000 800 600 -1 Frequency (cm )

Figure 97 . Top: B3LYP predicted IR spectra of ketenimine 204 ; middle: difference IR

spectra showing carbene 203 going away and ketenimine 204 forming; bottom: B3LYP predicted IR spectra of carbene 203 (A. Nikitina, unpublished results). “The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.” 162

3 371 353 (b) 440 336 2.5 480

(c)

2 390 Absorbance

1.5 (a)

200 300 400 500 600 700 Wavelength (nm)

Figure 98 . Matrix isolated UV-vis of diazirine 202, carbene 203, and ketenimine 204 (A.

Nikitina, unpublished results).

Scheme 67 . Matrix isolation study of diazirine 202

N h N 366nm N N N 334nm S Cl S Cl 313nm S Cl 10K, N2 202 203 204

Cl S 268

An intriguing result from O 2 trapping was observed by Nikitina and Sheridan in

the benzothiazolylchlorocarbene case. As expected, singlet benzothiazolylchlorocarbene 163

203 did not react with oxygen. Annealing an oxygen-doped N 2 matrix containing

ketenimine, however, generated a new product. Nikitina and Sheridan have proposed two

possible mechanisms for the oxygen trapping reaction with ketenimine 204 . Based on the

mechanism shown in Scheme 68, the generated product could be either 269 or 270 .

B3LYP predicted IR spectra of 270 nicely matched the experimental IR spectrum of the

generated product.

Scheme 68. Possible mechanisms of the formation of product 270 from 204 with O 2

Considering the fact that carbenes attached to thiazole rings have not been

reported by others and the ketenimine 204 generated by Asya and Sheridan from the

benzothiazolylchlorocarbene (203 ) showed different properties and chemistry than the

oxygen analogue, we synthesized and studied the benzothiazolyl(trifluoromethyl)-

diazirine (277 ) in low temperature matrices.

3.4.2 Synthesis of benzothiazolyl(trifluoromethyl)diazirine (277)

Benzothiazolyl(trifluoromethyl)ketone (273 ) was prepared following literature

procedure. 130 This procedure for making trifluoroacetyl ketones in heterocycles is unique 164

and follows Regel Buchus acylation mechanism. 131 Starting material benzothiazole ( 270 ) was dissolved in dry toluene, and trifluoroacetic anhydride (TFAA) was added dropwise at -20°C. After addition of TFAA, the reaction mixture solidified. Triethylamine (Et 3N)

was added dropwise, which turned the solid slowly into liquid again. The reaction

mixture was stirred at -20°C for 8 h and concentrated under reduced pressure at 50°C.

The obtained ketone matched the reported literature characterizations. Aqueous work-up

or just exposure to air converted ketone into hydrate.

The proposed mechanism is shown in Scheme 69. Nitrogen is first acylated with

TFAA to give 271 . Triethylamine then deprotonates the 2-position giving a carbene type

intermediate 272 and 1, 2 acyl shift occurs to give ketone 273 .

Scheme 69 . Possible mechanism for the synthesis of ketone 273

As CF 3 ketones attached to electron-deficient heterocycles often form hydrates

fairly easily, we developed a new method to make oximes from mixtures of ketones and

hydrates. The common method of using pyridine and hydroxylamine hydrochloride under

reflux condition was not efficient and clean, so Dean-Stark distillation was used. The

mixture of both ketone and hydrate was dissolved in dry toluene and hydroxylamine

hydrochloride and a catalytic amount of TsOH were added to the reaction mixture. The 165

mixture was distilled for 30 min, and after evaporation of solvent, the desired oxime 274

was isolated. This method was efficient, and both ketones and hydrates were converted

into oximes. The OH group of the oximes are sometimes clearly seen in 1H NMR spectra

and sometimes not observed for unknown reasons. One possible reason might be OH-

bonding to the basic N of benzothiazole, either intra or intermolecularly.

The oxime 274 was dissolved in dichloromethane and treated with triethylamine and a catalytic amount of dimethylaminopyridine, and stirred at room temperature for 15 min. p-TsCl was added portionwise (10min) keeping the reaction mixture at 0°C and the reaction mixture was stirred overnight. After work-up and evaporation of solvent, a yellowish solid tosyl oxime 275 was recovered which was further purified via

recrystallization in hexane and ether. The methyl group of the tosyl appeared at δ 2.48

1 ppm in the H NMR (CDCl 3) spectrum.

Diaziridine 276 was prepared by dissolving tosyl oxime in dichloromethane and

treating with excess liquid ammonia at -60°C for 5 h. Byproduct tosylamide was washed

out with water, and after evaporation of solvent under reduced pressure, crude diaziridine

was recovered. Contrary to usual diaziridine NH peaks, which appear as two doublets

with larger δ differences, the diaziridine NH peaks of 276 appear as a quartet at δ 3.16

ppm, due to a smaller δ difference.

Diazirine 277 was prepared by oxidation of diaziridine 276 with iodine and

triethylamine. The reaction was monitored via thin layer chromatography (TLC) and 166

NMR spectroscopy. The obtained solid diazirine 277 was purified by passing through a

silica plug. The complete synthetic procedure is shown in Scheme 70.

Scheme 70 . Synthesis of diazirine 277

3.4.3 Observation and characterization of syn and anti diazirine

Benzothiazolyl diazirine 277 was sublimed onto a cold (21 K) CsI window with

N2 in the ratio of 1: 800-1000 approximately. The IR spectrum of diazirine 277 in a N 2 matrix at 10 K showed major bands at 1640, 1622, 1614, 1560, 1525, 1504, 1475, 1459,

1439, 1429, 1348, 1336, 1313, 1282, 1274, 1247, 1233, 1210, 1195, 1190, 1180, 1166,

1082, 1071, 1056, 1045, 939, 896, 874, 830, 762, 736, 730, 714, 697, 662, 650, 590 and

541 cm -1. The experimental IR spectrum looked more complex than usual diazirines

(Figure 99) . Surprisingly, we found out that the experimental IR spectrum matches the 167

B3LYP predicted mixture of two conformers of diazirine, syn (CF 3 and sulfur), 277a, and anti (CF 3 and sulfur) 277b (Figure 100) .

1800 1600 1400 1200 1000 800 600

1750 1650 1550 1450 1350 1250 1150 1050 950 850 750 650 550 450 Frequency (cm -1)

Figure 99 . Top: B3LYP predicted IR spectra of syn and anti diazirine 277a and 277b in

relative intensities; bottom: matrix isolated IR spectrum of diazirine 277 in absorbance.

Figure 100 . Syn and anti diazirine, 277a and 277b . 168

The UV-vis spectrum of diazirine 277 at 10 K in the N 2 matrix showed

characteristic n π* absorptions at 376, 356, and 339 nm. However, no difference between

conformers was observed in the experimental UV-vis spectrum, although TD B3LYP

predicts a shift in anti diazirine 277b , 406 nm (f=0.0175) and 369 nm (f=0.0192) versus syn 277a , 381 nm (f=0.0252). Experimental UV-vis spectra best fit the predicted UV-vis spectra of 277a .

5.1

4.8

4.5

4.2

3.9

3.6

3.3

3 Absorbance

2.7

2.4

2.1

1.8

1.5

1.2 200 250 300 350 400 450 500 550 600 650 700 750 800 850 Wavelength [nm]

Figure 101. Solid line: Matrix isolated UV-vis spectrum of diazirine 277 ; solid bars: TD

B3LYP predicted UV-vis spectra of syn and anti diazirine 277a and 277b .

To the best of our knowledge no one has reported observation or characterization of two

conformers of a diazirine in any system. The two conformers have very distinct IR 169

vibrations showing strong bands at 1336, 1231, 1165, 1045 and 940 cm -1 for syn 277a

and 1348, 1195, 1190 and 890 cm -1 for anti 277b .

The presence of two conformers of diazirine 277 complicated the photochemistry

as well as the data analysis of the rearranged products. The diazirine was photo reactive

with three different wavelengths, 376, 366 and 334 nm. Irradiation of diazirine at 334 nm

destroyed both conformers of diazirine 277a and 277b (Figure 102), whereas short

irradiation at 376 or 366 nm (10min) destroyed mostly anti diazirine 277b . Complete

photolysis of diazirine 277 was not achieved with just one wavelength, but combination

of wavelengths removed most of the diazirine on longer term irradiation. Because of the

complicated photochemical reactons of diazirine 277 , we will mainly discuss in detail

one complete experiment, out of several we conducted.

Irradiation of diazirine 277 at 376 nm (10min) formed new IR bands at

1831(weak), 1583, 1542, 1471, 1420, 1413, 1385, 1330, 1318, 1291, 1279, 1254, 1227,

1208, 1198, 1182, 1173, 1157, 1147, 1134, 1125, 909, 900, 724, 690, and 670 cm -1

(Figure 103). The calculated IR spectra of singlet and triplet carbenes were very similar.

But, after careful examination, the generated IR bands were assigned mainly to a mixture of two conformers of triplet carbene. 170

Figure 102. Top: B3LYP predicted IR spectra of carbene 278a and 278b ; middle: difference IR spectra showing diazirine 277 going away and carbene 278 forming; bottom: B3LYP predicted IR spectra of syn and anti diazirine 278 . “The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.”

171

Figure 103. Middle: difference IR spectra showing anti diazirine 277b going away after irradiation at 376 nm (10 min); bottom: B3LYP predicted IR spectrum of anti diazirine

277b . “The difference IR spectrum is shown in relative absorbance units. The calculated

IR spectrum is shown in relative intensities.”

TD calculation of the UV-vis spectra of the triplet carbenes also matched better than singlets. The experimental UV-vis spectrum shows broad absorptions with maxima at 557, 466, and 426 nm (Figure 104). TD calculations for syn triplet carbene predicts absorption at 578 nm (f=0.0103) and for anti triplet carbene at 566 nm (f=0.0111), which are close to the experimental results. TD calculations for singlet carbenes are, syn at 476 172

nm (f=0.0220) and anti at 469 nm (f=0.0239). DFT calculation shows that triplet carbene is lower in energy than singlet which is again consistent with our prediction (see below in calculation discussion).

4.2

3.9

3.6

3.3

2.7

2.4 Absorbance

2.1

1.8

1.5

1.2

0.9 200 250 300 350 400 450 500 550 600 650 700 750 800 850 Wavelength [nm]

Figure 104. Solid line: matrix isolated UV-vis spectra of carbene 278 ; solid bars:

B3LYP predicted UV-vis spectra of syn and anti triplet carbene 278 .

3.4.4 Photochemical rearrangement of benzothiazolyl(trifluoromethyl)carbene

Longer irradiation of diazirine at 376nm (1 h) destroyed both conformers of carbene 278 and previously seen bands at 1831, 1386, 1141 and 940 cm -1 grew. The

B3LYP predicted IR spectrum of ketenimine 279 fit the matrix isolated IR spectra nicely.

Difference IR spectra show the carbene 278 and anti diazirine 277a were removed as

ketenimine 279 formed. Further irradiation (15 h) at 376nm completely destroyed

carbene 278, and anti diazirine 277b , and formed ketenimine 279 (Figure 105). However, 173

syn diazirine 277a is still left in the matrix along with ketenimine 279 . TD B3LYP predicts absorption at 463 nm (f=0.0162) for ketenimine 279 which matches the matrix isolated UV-vis of 279 (Figure 105).

Figure 105. Top: B3LYP predicted IR spectrum of ketenimine 279 ; middle: difference

IR spectra showing syn and anti carbene 278a and 278b going away and ketenimine 279 growing; bottom: B3LYP predicted IR spectra of syn and anti carbene 278a and 278b .

“The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.” 174

Subsequent irradiation at 578 nm (22 h) generated more ketenimine 279 along

with distinct new bands at 2189, 1331, 1290 and 1150 cm -1. These new bands fit the

calculated IR spectra of quinoimine 280 (Figure 106). TD B3LYP predicts absorption at

561 nm (f=0.0589) for quinoimine 280. The UV-vis spectrum (Figure 107) shows both

279 and 280 clearly.

Interestingly, the difference IR spectra show syn diazirine 277a disappearing and

forming ketenimine 279 and quinoimine 280 . Surprisingly, syn diazirine appears to be

photoreactive at 578nm. Usually, diazirines do not absorb at these long wavelength. We

speculate that shorter wavelength light might have been leaking at 578nm. However, it

appears that on irradiation, ketenimine 279 ring opens to 280 as expected. 175

Figure 106. Top: B3LYP predicted IR spectra of ketenimine 279 and quinoimine 280 ; middle: difference IR spectra showing syn diazirine 277a going away and 279 and 280 growing; bottom: B3LYP predicted IR spectrum of syn diazirine 277a . “The difference

IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.”

176

4.2

3.8

3.6

3.4

3.2 Absorbance 3

2.8

2.6

2.4

2.2

2 200 250 300 350 400 450 500 550 600 650 700 750 800 850 Wavelength [nm]

Figure 107. Matrix isolated UV-vis spectrum of ketenimine 279 (major) and quinoimine

280 (minor).

Irradiation of the matrix containing 279b and 280 at 435nm (24 h) shows the

bands at 1831 (broad), 1385, 1199 and 1146 cm -1 disappearing and forming new bands at

1816 (broad), 1389, 1195, 1137 cm -1. Warming the matrix to 20 K caused these bands to

revert back to the original 279 IR absorption (Figure 108). We believe that, these two

different set of IR bands correspond to the same intermediate 279 but of different

conformers. Since, the ketenimine 279 is formed in a rigid chiral pocket, the

photochemically induced conformational change product doesn’t fit into the same rigid

pocket, and we see slight changes in frequencies. On warming, the matrix anneals back to

the initial “fit”. Similar shifts should be observed in the matrix isolated UV-vis spectra

too, but we were not able to observe any distinct changes in the matrix isolated UV-vis

spectra. Analogous observation were made in the chloro ketenimine (A. Nikitina

unpublished results). 177

1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800

-1 Frequency (cm )

Figure 108 . Difference IR spectra showing conformational change of ketenimine 279a to

279b and vice versa in relative absorbance units.

Separate experiments revealed that irradiation at 366 nm (12+ h) slowly destroyed both the intermediates, 279 and 220, and formed both conformers of carbene 278 . Slow

conversion of ketenimine 279 to quinoimine 280 was also observed at 313 nm and vice

versa at 546 nm. As discussed in the background section, ring opened product quinoimine

280 is believed to be the intermediate involved in the formation of ketenimine 279 from

carbene 278. 178

So, in the benzothiazole case, we were able to observe, and characterized both conformers of diazirine, syn 277a and anti 277b . The photochemistry of diazirine 277 in

low temperature matrices was complicated (Scheme 72) as both syn 277a and anti 277b were photolyzed at different wavelength, selectively. Short irradiation of 277 at 334, 366

or 376 nm generated carbene 278 . The carbene 278 rearranged into cyclic ketenimine 279 and ring opened product 280 . Intermediates, 279 and 280 photochemically interconvert.

Conformational change of ketenimine 279 was observed both thermally and

photochemically.

Scheme 71. Photochemical reactions of diazirine 277

179

3.4.5 Trapping reactions of benzothiazolyl(trifluoromethyl)carbene

Trapping reactions of benzothiazolyl(trifluoromethyl)carbene were conducted in low temperature N 2 matrices both with O 2 and HCl. Diazirine 277 was sublimed onto a

cold CsI window (21K) with N 2 containing 1-5% of O 2. Irradiation of the O 2 doped

nitrogen matrix at 334 nm generated a complex array of products. It appeared carbene

278 reacted with O 2 even at 10 K and generated several products giving complex sets of

IR bands. An intense IR band at 1218 cm -1 closely matched the predicted IR spectra of

carbonyl oxide 281 . Annealing the N 2 matrix at 30 K led to disappearance of some IR

bands and growth of some already existing IR bands such as 1218 cm -1. The experimental

UV-vis spectra showed a strong absorption around 400-450 which is characteristic of

formation of carbonyl oxide. When the carbonyl oxide was irradiated at 404 nm, the

intense absorption in UV-vis spectra disappeared and most presumably it made dioxirane

282 . Though IR showed some changes, it was very difficult to characterize carbonyl

oxide 281 and dioxirane 282 via IR as the vibrations of both intermediates are predicted

to be very close to each other in the benzothiazolyl case (Figure 109). 180

500 450 400 350 300 250

Intensities 200 150 100 50 0 1800 1550 1300 1050 800 550

Frequency (cm -1)

Figure 109 . B3LYP predicted IR spectra of carbonyl oxide 281 (blue) and dioxirane 282

(red).

Diazirine was also sublimed onto a cold CsI window (21K) with N 2 containing

2% of HCl. Irradiation of diazirine at 334 nm generated carbenes, quinoimine and new IR

bands. Surprisingly, no ketenimine bands were seen. So, the new bands could possibly be

the HCl addition product of ketenimine, but we don’t have conclusive evidence for that.

Annealing the matrix at 30 K did not change the carbene IR spectrum and no HCl

addition product was observed. This further confirms that the generated carbene 278 is a

ground state triplet. The overall trapping reaction results are shown in Scheme 73.

181

Scheme 72 . Trapping reaction of carbene 278 with O 2 and HCl

3.4.6 Study of C 9H4N3F3S potential energy surface

B3LYP calculation predicts that ground state triplet carbene 208 is approximately

5 kcal/mol lower than singlet state, which is consistent with our spectroscopic evidence

and trapping reaction results. This is contrary to the chloro case, where carbene 202 is a

ground state singlet. Both singlet 202 and triplet 278 do similar photochemistry in low

temperature matrices. B3LYP calculation predicts that, compared to chloro quinoimine

203 which is 16 kcal/mol higher than carbene 202 , benzothienyl(trifluoromethyl)-

quinoimine 280 is only 7 kcal/mol higher than carbene 278. This might be the reason why

chloro quinoimine 203 was not observed by Nikitina and Sheridan, as it might be

energetically less favorable. The C=C=N stretching vibration around 1831 cm -1 shows

that the ketenimine 279 is more allenic in character compared to 1558 cm -1 in the

didehydrochloro benzoxazine 199 . Unpublished results by Nikitina and Sheridan show a

similar vibration around 1800 cm -1 in chloro ketenimine, 204 . Previous reports from the 182

Sheridan group indicate that longer C-S bond lengths and smaller C-S-C bond angles in cyclic thiocumulenes accomodate allenic geometries more than their oxygen analogues. 108 Contrary to the didehydrobenzoxazine 199 , in the sulfur analogues,

restricted B3LYP calculations fit the experimental IR spectra of CF 3 ketenimine 279,

which is again consistent with chloro ketenimine 204. Moreover, we could not locate a

lower energy open shell singlet in 279 .

Figure 110. B3LYP predicted energies of carbene 278 and 202 and their rearrangement

products. 183

We have successfully synthesized benzothiazolyl(trifluoromethyl)diazirine (277 )

and generated, observed and characterized the corresponding carbene 278 and its

rearrangement products in low temperature matrices. Contrary to the chloro analogue

202, CF 3 carbene 278 is a triplet. Formation of ketenimine 279 from benzothiazolyl-

(trifluoromethyl)carbene 278 is consistent with Nikitina and Sheridan’s chloro carbene

203 rearrangement results. But in the CF 3 case, we were able to observe and characterize

the ring-opened intermediate, thioquinoimine 280 which was not observed or

characterized in the chloro case. However, we were not able to find a wavelength of

irradiation that gave selective conformations of carbene 278a or 278b or quinoimine 280 .

Also, we were not able to observe carbene 278 rearranging into quinoimine 280 . Most

interestingly, we were able to observe and characterize both syn and anti conformers of

diazirine 277 in a low temperature nitrogen matrices, and do selective photolysis at

different wavelength.

3.5 Benzoxazolyl(trifluoromethyl)carbene

To compare and contrast chloro versus CF 3 substitution we synthesized and

studied the benzoxazolyl(trifluoromethyl)diazirine 288 also in low temperature matrices.

3.5.1 Synthesis of benzoxazolyl(trifluoromethyl)diazirine

Benzoxazolyl(trifluoromethyl)ketone (284) was prepared following a similar

procedure as benzothiazolyl(trifluoromethyl)ketone (273) following literature 184

procedure. 126 Starting material 283 was dissolved in dry toluene and trifluoroacetic

anhydride (TFAA) was added dropwise at -35°C. After addition of TFAA, the reaction

mixture became solid. Triethylamine (Et 3N) was added dropwise, which turned the solid slowly into liquid again. The reaction mixture was stirred at -19°C for 8 h. Because of the tendency of the bezoxazolyl(trifluoromethyl)ketone to form hydrate, aqueous work-up was avoided and the mixture was concentrated under reduced pressure. After the concentrated mixture was brought to room temperature, the product slowly formed fine crystals. We found that the ketone 284 dissolves in chloroform whereas hydrate doesn’t.

A crystal structure of the ketone 284 was obtained for characterization purpose. 1H, 19 F and 13 C NMR matched the reported literature values.

We used the Dean-Stark method similar to benzothiazole to prepare benzoxazolyl(trifluoromethyl)oxime 285 by treating ketone 284 with hydroxylaminehydro- chloride and refluxing in toluene. Azeotrope of water and toluene was collected in the

Dean Stark trap as a viscous liquid. The remaining reaction mixture containing excess hydroxylamine as a solid was filtered and solvent removed under reduced pressure giving clean oxime 285 .

The tosyloxime 286 was prepared by following the usual procedure of treating oxime with triethylamine and a catalytic amount of dimethylaminopyridine and p-TsCl.

The reaction mixture turned yellow after 2 h of stirring. After work-up and concentration of solvent, yellow solid was recovered which showed tosyl peaks in the 1H NMR

(CDCl 3) with the methyl peak at δ 2.49 ppm. 185

Diaziridine 287 was prepared by treating tosyl oxime 286 with liquid ammonia at

-78°C using the same procedure used to prepare benzothiazolyl(trifluoromethyl) diaziridine ( 276 ). The 1H NMR for diaziridine NHs showed two doublets appearing at δ

3.03 ppm and 3.33 ppm.

Diazirine 288 was obtained by oxidation of benzoxazolyl(trifluoromethyl) diaziridine (287 ) with iodine and triethylamine, using the same procedure described for benzothiazolyl(trifluoromethyl)diazirine (277 ). The diazirine was characterized by 1H

NMR, 13 C NMR and UV-vis spectra. The complete synthetic procedure is shown in

Scheme 73.

Scheme 73. Synthesis of diazirine 288

1. TFAA, Toluene, OH O NH OH.HCl, Toluene N o 2 N N -35 C, 45min N TsOH o 2. Et3N, -19 C, 6h CF3 CF3 O O O 284 Dean-Stark Reflux 285 283 lit. 65% 30min, 80%

Et N, DMAP,CH Cl OTs H 3 2 2 N N p-TsCl N Liquid NH3, CH2Cl2 N N CF3 H o o O 0 C, 5 h, 87% O -78 C, 5 h, 71% CF3 286 287

N I2, Et3N, CH2Cl2 N N 0oC, 30min, 62% O 288 CF3

186

3.5.2. Observation and characterization of syn and anti diazirine 288

o Benzoxazolyl(trifluoromethyl)diazirine (288 ) was sublimed from -10 C to +5 °C

onto the cold CsI window (21 K) with 60-100 torr of N 2. The obtained IR spectrum

(Figure 111) showed major IR bands at 1621, 1574, 1454, 1381, 1361, 1330, 1298, 1294,

1279, 1262, 1243, 1237, 1210, 1204, 1198, 1194, 1192, 1186, 1182, 1067, 1021, 1003,

984, 981, 913, 909, 884, 800, 791, 762, 750, 727 and 624 cm -1.

Absorbance

1750 1650 1550 1450 1350 1250 1150 1050 950 850 750 650 550 450

-1 Frequency (cm )

Figure 111. Matrix isolated IR spectrum of benzoxazolyl(trifluromethyl)diazirine (288 ).

187

After comparison with B3LYP predicted spectra, it was confirmed that the experimental IR spectrum shows bands for both syn and anti -conformers of diazirine 288 .

Thus, as in the benzothiazole case, both conformers of diazirine 288 were observed in low temperature N 2 matrices (Figure 112).

The experimental UV-vis of diazirine shows n π* absorption at 358, 342 and 326

nm which is little bit shifted from predicted TD calculation for syn 288a (oxygen syn to

CF 3) at 390 nm and anti 288b (oxygen anti to CF 3) at 407 nm. The UV-vis spectra of diazirine in low temperature matrices is shown in Figure 113 and B3LYP predicted UV- vis spectra both syn and anti diazirine, 288a and 288b are shown in Figure 114. 188

1800 1600 1400 1200 1000 800 600

1750 1650 1550 1450 1350 1250 1150 1050 950 850 750 650 550 450

-1 Frequency (cm )

Figure 112 . Top: B3LYP predicted IR spectra of syn and anti diazirine 288 ; bottom: matrix isolated IR spectrum of diazirine 288 . “The matrix isolated IR spectrum is shown in absorbance units. The calculated IR spectrum is shown in relative intensities.”

189

.Figure 113. Matrix isolated UV-vis spectrum of benzoxazolyl(CF 3)diazirine (288 ).

0.3

0.25

0.2

0.15

0.1 Absorbance

0.05

0 200 300 400 500 600 Wavelength (nm)

Figure 114. B3LYP predicted IR spectra of syn and anti diazirine 288

3.5.3 Observation and Characterization of Benzoxazolyl(CF 3)carbene

Benzoxazolyl(CF 3)diazirine 288 was photoreactive at 313, 334, and 366 nm.

Even a short irradiation (5min) at 334 nm destroyed diazirine 288 bands and new IR 190

bands were formed (Figure 115). At the same time, the matrix window turned orange.

The IR spectrum showed bands at 2175, 2131, 1666, 1598, 1567, 1477, 1436, 1426,

1396, 1375, 1342, 1313, 1284, 1276, 1249, 1220, 1207, 1202, 1189, 1185, 1178, 1153,

1138, 1132, 1108, 1074, 973, 948, 871, 816, 772, 765, 745, 682, 617, 598, 590 and 556 cm -1.

Figure 115. Difference IR spectra of benzoxazolyl(CF 3)diazirine (288 ) going away at

334nm (5min) and new products forming shown in relative absorbance.

Comparison of experimental IR spectra with predicted B3LYP spectra fit the triplet carbene 289 better than singlet carbene (Figure 116). This comparison also indicates that both syn 289a , and anti 289b , isomers of carbene are present in the matrix. 191

The B3LYP predicted energy of carbenes are also consisted with spectroscopic result, as triplet carbene is predicted to be lower in energy than singlet carbene (will discuss below). Despite several irradiation attempts, generation of selective conformation of carbene 289a and 289b was not achieved.

400

350

300

250

200

Intensities 150

100

0 2300 2100 1900 1700 1500 1300 1100 900 700 500

Frequency (cm -1)

Figure 116. B3LYP predicted IR spectrum of benzoxazolyl(CF 3) triplet carbene, both syn and anti conformer, 289a and 289b .

The experimental UV-vis spectrum after irradiation at 334 nm for 5 min shows a

broad peak with maxima at 445 nm and tailing up to 560 nm (Figure 17). TD B3LYP

calculation of triplet carbene absorptions are for syn 502 nm (f=0.0108), 494 nm

(f=0.0004), 442 nm (f=0.0004) and 426 nm (f=0.1154) and for anti 500 nm (f=0.0106), 192

496 nm (f=0.0007), 441 nm (f=0.003), and 425 nm (f=0.1174) (Figure 118). So, the experimental UV-vis absorptions are close to predictions.

5.2

4.8

4.4

3.6

3.2 Absorbance 2.8

2.4

1.6

1.2

0.8 200 250 300 350 400 450 500 550 600 650 700 750 800 850 Wavelength [nm]

Figure 117 . Experimental UV-vis spectrum after irradiation of diazirine 288 at 334nm for 5 min in nitrogen matrices.

0.16

0.14

0.12

0.1

0.08

0.06

0.04 Absorbance

0.02

0 200 300 400 500 600 Wavelength (nm)

Figure 118. TD B3LYP predicted UV-vis spectra of syn and anti carbene 289a and 289b .

193

3.5.4 Photochemical rearrangement of benzoxazolyl(trifluoromethyl)carbene

Irradiation of the orange colored matrix containing benzoxazolyl carbene 289 at

435 nm or 546 nm (1+ h) bleached both conformers of carbene and IR bands at 2175,

1667, 1426, 1313, 1310, 1285, 1141, 1128, 1073, 1034, 878, 872, and 734 cm -1 which

were present with the formation of carbene, grew. At the same time, the color of the

matrix changed from orange to yellow. Comparing to possible rearrangement products,

the experimental IR spectra fit the B3LYP predicted spectra of quinoimine 290 (Figure

119). TD B3LYP calculated UV-vis spectra of quinoimine 290 shows strong absorption at 467 nm (f=0.0980) and 328 nm (f=0.2466). The experimental UV-vis spectra of quinoimine shows strong absorption around 340 nm and above 400 nm tailing to 470 nm, which is close to predicted UV-vis spectra (Figure 120). 194

2300 2100 1900 1700 1500 1300 1100 900 700 500

2300 2100 1900 1700 1500 1300 1100 900 700 500 -1 Frequency (cm )

Figure 119. Top: B3LYP predicted IR spectrum of quionimine 290 ; middle: difference

IR spectra showing carbene 289 going away and quionimine 290 forming; bottom:

B3LYP predicted IR spectra of carbene 289 . “The difference IR spectrum is shown in relative absorbance units. The calculated IR spectra are each shown in relative intensities.” 195

Irradiation of quinoimine 290 at 354 nm for 2+ h lowly converted it back to carbene 289 . The overall photochemical reaction of diazirine 288 in low temperature matrices is shown in Scheme 74.

Figure 120 . Solid line: Matrix isolated UV-vis spectra of quinoamine 290 ; solid bars: TD

B3LYP 6-31+G** predicted UV-vis spectra of quinoamine 290 .

Scheme 74. Matrix isolation study of benzoxazolyl(trifluoromethyl)diazirine 288

N N N N N O 366nm N N CF3 + + CF3 CF3 O N 10K O CF3 O 288a 288b 289a 289b

435nm N N

CF3 354nm O O CF3 290 291 196

Contrary to the chloro case, in the CF 3 case we were not able to observe or

characterize ketenimine 291 in low temperature matrices. We did see some evidence of a

C=C=N vibration around 1750 cm -1 in the IR spectra, possibly corresponding to

ketenimine 291 , when diazirine 288 was irradiated at 334 nm (Figure 123). B3LYP

predicted calculation shows ketenimine 291 vibration around 1740 cm -1. But, we were

unable to generate and characterize ketenimine 291 selectively. TD B3LYP calculation

predict absorption at 587 nm (f=0.0194), 373 nm (f=0.005) and 354 nm (f=0.0886) which

comes close to experimental UV-vis spectra after irradiation of diazirine 288, shown in

Figure 117. The B3LYP predicted IR spectra and UV-vis spectra ketenimine 291 are

shown in Figure 121 and 122.

400 350 300 250 200 150 Intensities 100 50 0 1800 1600 1400 1200 1000 800 600

Frequency (cm -1)

Figure 121. B3LYPpredicted IR spectra of keteinimine 291 . 197

0.1

0.08

0.06

Absorbance 0.04

0.02

0 200 300 400 500 600 Wavelength (nm)

Figure 122. TD B3LYP predicted UV-vis spectra of keteinimine 291 .

Figure 123. Difference IR spectra after irradiation of diazirine 288 at 334 nm shown in relative absorbance. Red arrow shows the IR band around 1750 cm -1.

198

Nikitina and Sheridan reported that when chloroquinoimine 198 was irradiated at 404

nm, ketenimine 199 was generated which fit unrestricted calculations of UB3LYP predicted IR spectra. In the CF 3 case, both restricted and unrestricted B3LYP calculation

predicts similar IR spectra but unrestricted predict slightly lower energy than restricted.

However, we were not able to observe and characterize ketenimine 291 . One of the possible explanations is that ketenimine IR bands might be overlayed with carbene and quinoimine bands. The B3LYP predicted IR spectra for ketenimine 291 do overlap with carbene and quionoimine bands. An unpublished result by Wang and Sheridan in the CF 3

benzofuran case shows that quinomethide doesn’t ring close to make cumulene. But, the

effect of CF 3 on ketenimine is still unclear

3.5.5 Trapping reaction of benzoxazolyl(trifluoromethyl)carbene

Benzoxazolyl(trifluoromethyl)diazirine 288 was sublimed onto cold CsI window

(21K) with nitrogen doped with O 2 (1-2%). Irradiation of 288 at 366 nm for 15 min at 10

K destroyed diazirine IR bands and a new set of IR bands were formed. These new bands

were different than previously seen carbene bands. The complex IR spectra were difficult

to analyze and characterize a specific trapping product. So, even at 10 K, apparently

carbene reacts with O 2. This oxygen trapping reaction is consistent with the CF 3

benzothiazole case. Based on the reaction in the benzothiazole system, the trapping

reaction can be summarized as shown in Scheme 75.

199

Scheme 75. Trapping reaction of carbene 289 with O 2

3.5.6 Study of C 9H4N3F3O potential energy surface

B3LYP calculated energies of potential intermediates in the benzoxazolyl(trifluoromethyl)carbene system show that the triplet carbenes are lower in energy than singlets.

Both ketenimine 291 and quinoimine 290 are lower in energy than carbene 289 . Also, the

energy difference between carbene 289 and ketenimine 291 is less than 2 kcal/mol which

might be related to why we were having difficulty in isolating and observing ketenimine

290 , even in low temperature matrices. In the chloro case, singlet carbenes are lower in energy than triplets, and both ketenimine 199 and quinoimine 198 are higher in energy

(Figure 124). This shows that substitution changes electronics of these intermediates in this case substantially. 200

Figure 124. B3LYP predicted energies of benzoxazolyl(trifluoromethyl)carbene 289 and

benzoxazolylchlorocarbene 197 and their rearrangement products.

The low temperature behavior of benzoxazolyl CF 3 diazirine 288 is consistent

with benzoxazolylchlorodiazirine 196 reported by Nikitina and Sheridan only to some extent. Chloro diazirine 196 was also photoreactive at 334 nm and generated carbene 197

and additional product even within short irradiation time. But, contrary to benzoxazolyl 201

chlorocarbene 197 which is singlet, benzoxazolyl CF 3 carbene 289 is ground state triplet.

But, in chloro case, the observation of two conformers of diazirine was not observed or characterized in either benzothiazole or benzoxazole system.

In conclusion, we have successfully synthesized benzoxazolyl(trifluoromethyl)diazirine (288 ) and generated, spectroscopically observed and characterized benzoxazolyl(trifluoromethyl)carbene ( 289 ). Similar to our observation in the CF 3 benzothiazole case, we observed both conformers of diazirine 288 . Also, very short

irradiation of diazirine generates carbene 289 along with ring opened product 290 .

Although we have some possible spectroscopic evidence for the C=C=N vibration of

ketenimine, we were not able to characterize ketenimine in low temperature matrices.

3.6 Conclusions

Overall, we have been successful in studying a variety of previously unexplored 5- membered heteroaryl carbenes. In the case of 3-benzothiophene, we were able to unravel a plethora of carbene rearrangement products, such as bicyclic product 232 , ring expanded carbene 233 , and spiro product 234 and characterized them spectroscopically.

More importantly, we were able to introduce the UV-vis transparent diazirine, which

might be important for applications of photoaffinity labeling agents. Similarly, we were

able to synthesize the indole diazirines and produced and characterized carbenes 245 and

260 in low temperature matrices for both 2- and 3- isomers, respectively. Similar to the 2-

benzothienyl(trifluoromethyl)case, 3-benzothienyl and both 2-and 3- indolyl(trifluoro-

methyl)carbenes were ground state singlets. We were also able to study the chloro vs. 202

trifluoromethyl group affect in both benzothiazole and benzoxazole cases. Contrary to the chloro cases, these trifluoromethyl carbenes are ground state triplets in both benzothiazole and benzoxazole. Furthermore, we were able to observe and characterize both syn and anti conformer of diazirines via IR spectra in both the benzothiazole and benzoxazole cases.

203

3.7 Experimental

3.7.1 General

All solvents and commercially available starting materials were purchased from

Sigma-Aldrich, and used without further purification, unless otherwise noted. All NMRs

(1H NMR, 13 C NMR and 19 F NMR) were recorded on Varian (MR 400 MHz, V400 MHz, and V 500 MHz) spectrometers. Chemical shifts ( δ) of the NMR spectra are recorded in parts per million (ppm) relative to tetramethylsilane(TMS) as internal standard for 1H

13 19 NMR and C NMR, and CDCl 3 for F NMR . Flash column chromatography and silica plug filtration was performed using silica gel F60 (230-400 mesh). Thin Layer

Chromatography (TLC) was performed using glass backed silica gel (250 µm) and

visualized with ultra-violet light (254 nm). Mass spectra were taken on an Agilent GC-

MS instrument. All recorded IR and UV-vis spectra were taken on a Perkin Elmer 2000

FT-IR spectrometer with 1 cm -1 resolution and a Perkin Elmer Lamda 850 UV-vis

spectrometer respectively. Crystal structures were taken on a Bruker SMART CCD area detector X-ray diffractometer.

3.7.2 Matrix Isolation

All matrix isolation experiments were performed on a mobile Displex refrigerator system assembled by the Sheridan group. The Displex unit comprises a DE-202 closed cycle helium refrigerator (expander), and an APD Cryogenics compressor. The expander 204

has a window holder, surrounded by a vacuum shroud. The window holder is attached to the cold tip, and an indium gasket is placed between window holder and the cold tip for good thermal contact. A high vacuum pump is used to ensure vacuum between the expander and the shroud. The general details of the matrix isolation apparatus have been reported previously. 65 The window temperature was measured using either a 0.07 % iron-doped gold vs chromel thermo couple, or Si diode sensor, imbedded in the cold-tip adjacent to the window holder, and connected to a Scientific Instruments Inc. temperature indicator/controller. This unit operated a 25-W resistive heater which allowed for thermal regulation of the cryostat at preset temperature. The flow rate to the cold finger was controlled by a variable leak valve and pressure measured by a differential pressure gauge (PDR-C-2C, MKS Instrument Inc.). Monochromatic irradiation of the matrices was provided by a Photon Technologies Inc. 01-001 Series system with a HBO 100 W

Hg high pressure lamp.

All diazirines were deposited onto the matrix using “direct deposition” procedures.

Diazirines, were dissolved in dichloromethane, and condensed either using water pump aspirator, or low temperature vacuum distillation. Diazirines were transferred into a deposition tube and connected to the sample inlet tube connected to the refrigerator shroud. The gas handling system was evacuated to 10-3 torr and the glass manifold was filled with approximately 400-450 torr of nitrogen gas. The deposition tube containing diazirine was cooled with liquid nitrogen and air was removed using a “freeze-thaw- pump” method, usually three times. Once the pressure remained constant, diazirines were 205

sublimed onto a 2.5 cm CsI window at 21 K along with the inert gas (Nitrogen) at a rate of 1 torr/min. Trapping reagents (Oxygen and HCl) were prepared in the 3 L glass manifold (1-5 %) and were added before mixing with nitrogen. Typical inert gas to diazirine ratio was estimated to be ca. 500-1000:1. Standard experiments consisted of

100-150 torr of nitrogen. After completion of deposition, the window was cooled to the lowest temperature (10 K) and IR and UV-vis spectra were taken. The matrices containing diazirine were irradiated at different wavelengths and reaction monitored by

IR and UV-vis spectroscopy. Annealing experiments were done by regulating the temperature with the resistive heater and annealing the matrix from 20-35 K. All spectra were taken at 10-12 K, except the annealing experiments.

3.7.3 DFT Calculation

All structures were fully optimized by analytical gradient methods using the

Gaussian03 suites and B3LYP Density Functional Theory (DFT) calculations with a 6-

31+G(d,p) basis set.24 Energies were corrected for zero-point energy differences (ZPVE)

(unscaled). Vibrational analyses established the nature of all stationary points as either

energy minima (no imaginary frequencies) or 1st order saddle points (one imaginary

frequency). Excited state calculations were performed via the Time-dependent DFT

method implemented in the Gaussian programs, using TD B3LYP methodology with the

6-31+G(d,p) basis set on ground-state geometries optimized at the same level. Optimized 206

coordinates, energies, imaginary frequencies for transition states, and TD results are listed below

3.7.4 Synthesis

1-(Benzo[b]thiophen-3-yl)-2, 2, 2-trifluoroethanone (227) 120,121,132

3-Bromobenzothiophene (226 ) (6.6 g, 31 mmol) was dissolved in dry Et 2O (125 mL) and

stirred at -70 °C (ethanol and liquid nitrogen bath) under argon atmosphere. t-BuLi (40

mL, 68 mmol, 1.7 M pentane) was added dropwise (21 min) stirring the reaction mixture

at -70 °C. The reaction mixture was stirred at -70 °C for 30 min. CuBr(Me) 2S (6.5 g, 31

mmol) was added in one portion at -70 °C. The reaction mixture was stirred for 30 min

at -70 °C and trifluoroacetic anhydride (TFAA) (5 mL, 35 mmol) was added dropwise at

-35 °C. The reaction mixture was stirred at -20 °C for 8 h. Saturated NH 4Cl (4 g, 50 mL) was added dropwise at -70 °C and left stirring while the cold bath naturally warmed for

8 h. The temperature of the cold bath after 8 h was +12 °C. The reaction mixture was brought to room temperature and washed with ether and water. The organic phase was separated, dried over MgSO 4, and condensed under reduced pressure. Crude product (5.7 g, 80 %) was obtained, which formed nice needle shaped crystals (1.92 g) at room temperature along with (3.78 g) viscous liquid. Combined crude product was used in subsequent steps. An X-ray crystal structure of the ketone 227 was obtained. MS (EI)

+ 1 m/z: 230(M ); mp. 44.8-48 °C; H NMR (400 MHz, CDCl 3, ppm) δ 8.77-8.72 (d, J=8.2

Hz, 1H), 8.66-8.62 (q, J=1.7Hz, 1H), 7.94-7.90 (d, J=8.1 Hz, 1H), 7.60-7.48 (m, 2H); 207

13 C NMR (125 MHz, CDCl 3, ppm), 174.2 (q), 142.4 (q), 139. 1, 136.5, 127.3, 126.7,

19 126.4, 125.2, 122.4, 113.0(q); F NMR (376 MHz, CDCl 3, ppm) δ −72.03.

1-(Benzo[b]thiophen-3-yl)-2, 2, 2-trifluoroethanone oxime (228)

Crude ketone 227 (0.95 g, 4 mmol) was dissolved in ethanol (10 mL), pyridine (5 mL)

was added and the reaction mixture was stirred at room temperature for 5 min. The

hydroxylamine hydrochloride (NH 2OH.HCl) (0.86 g, 12 mmol) was added in one portion

to the reaction mixture and refluxed for 15 h under nitrogen atmosphere. The reaction

mixture was allowed to come to room temperature and concentrated under reduced

pressure to remove pyridine. The concentrated product was dissolved in dichloromethane

(CH 2Cl 2) and washed with saturated citric acid. The organic phase was separated, dried over anhydrous MgSO 4, and solvent removed under reduced pressure. Crude product 228

(0.92 g, 90 %) was recovered which was used for the next step after unsuccessful

attempts to separate syn and anti isomers. MS (EI) m/z: 245(M +); 1H NMR (400 MHz,

CDCl 3, ppm) δ 8.73-8.69 (s, 1H), 8.53-8.48 (s, 1H), 8.05-8.01 (d, J=8.0 Hz, 1H), 7.95-

7.85 (m, 2H), 7.75-7.72 (s, 1H), 7.69-7.66 (s, 1H), 7.65-7.61 (m, 1H), 7.47− 7.38( m,

13 4H); C NMR (125 MHz, CDCl 3, ppm) δ 143.99, 139.56, 139.26, 129.8 (q), 128.74 (q),

125.13, 125.09, 125.04, 124.76, 123.59, 123.53, 122.67, 122.65, 122.19, 121.87, 121.59,

19 119.41, 119.26; F NMR (376 MHz, CDCl 3, ppm) δ −67.91, −62.94 .

1-(Benzo[b]thiophen-3-yl)-2, 2, 2-trifluoroethanone O-tosyl oxime (229)

Crude oxime 228 (0.92 g, 3.7 mmol) was dissolved in CH 2Cl 2 (10 mL). Et 3N (1 mL, 7.5 mmol) and a catalytic amount of dimethylaminopyridine (DMAP) were added and stirred 208

at 0 °C for 5 min. p-TsCl (0.72 g, 3.7 mmol ) was added portionwise (5 min) and stirred at 0 °C for 12 h. The mixture was washed with water and extracted with CH 2Cl 2. The organic phase was separated, dried over anhydrous MgSO 4 and solvent removed under reduced pressure. Crude product 229 was recovered, and purified by column chromatography (1:8 EtOAc/hexane) (1.22 g, 81 %). From 1H NMR, it looked like only

one isomer of tosyl oxime 229 was isolated. MS (EI) m/z: 399(M +); mp 115.4-132.9 °C

1 ; H NMR (400 MHz, CDCl 3, ppm) δ 7.92-7.86 (m, 3H), 7.69-7.67 (s, 1H), 7.47-7.38

19 (m, 4H), 7.36-7.32 (m, 1H), 2.52−2.49(s, 3H); F NMR (376 MHz, CDCl 3, ppm) -

13 68.1; C NMR (125 MHz, CDCl 3, ppm) : 150.3-149.4 (q), 146.27, 139.21, 135.79,

131.17, 130.25 (q), 129.90, 129.35, 125.47, 125.28, 122.99, 122.76, 120.6, 120.34, 21.84.

3-(Benzo[b]thiophen-3-yl)-3-(trifluoromethyl)diaziridine (230)

Purified tosyl oxime 229 (1.0 g, 2.5 mmol) was dissolved in CH 2Cl 2 (15 mL). The

reaction mixture was stirred at -60 o C (ethanol and liquid nitrogen) and ammonia gas

(NH 3) was added and condensed to liquid ammonia, approximately 50 mL. The reaction

mixture was stirred for 18 h at -60 °C. The cold bath was removed and left at room

temperature to allow NH 3 to evaporate for 5 h. The reaction mixture was washed with water (75 mL) and CH 2Cl 2 (100 mL). The organic phase was separated and dried over

Na 2SO 4, and solvent was removed under reduced pressure. Column chromatography (1:

23 EtOAc/hexane) gave pure diaziridine as a solid (0.2 g, 32 %). MS (EI) m/z: 244(M +);

1 H NMR (400 MHz, CDCl 3, ppm) δ 8.03-7.96 (d, J=8.0 Hz, 1H), 7.92-7.86 (d, J=4.0 Hz

1H), 7.82-7.77 (s, 1H), 7.48-7.38 (d, J=8.0 Hz, 2H), 2.90-2.80 (d, J=12.0 Hz, 1H), 209

13 2.45−2.35 ( d, J=12.0 Hz, 1H); C NMR (100 MHz, CDCl 3, ppm) δ 140.0, 137.1, 129.8,

19 126.9, 125.1, 124.9, 122.9, 122.5 (q), 123.5 ( q), 55.0 (q); F NMR (376 MHz, CDCl 3,

ppm) -76.65.

3-(Benzo[b]thiophen-3-yl)-3-(trifluoromethyl)-3-H-diazirine (223)

Diaziridine 230 (0.1 g, 0.4 mmol) was dissolved in CH 2Cl 2 (4 mL) and stirred at 0 °C.

Et 3N (0.22 mL, 1.6 mmol) was added and the reaction mixture was stirred for 5 min.

Iodine (0.1 g, 0.4 mmol) was added portion wise (3 min) and the reaction mixture stirred

for 1 h at 0 °C. The reaction mixture was washed with sodium hydroxide solution (10mL)

and CH 2Cl 2 (30mL). The organic phase was separated, dried over Na 2SO 4, and solvent

removed under reduced pressure. Silica gel column chromatography (hexane) yielded

1 (0.07g, 70 %) diazirine 223 . H NMR (400 MHz, CDCl 3, ppm) δ 8.08-8.12 (d, J=8.0 Hz,

1H) 7.85-7.90 (m, J=8.0 Hz, 2H), 7.40−7.50 (m, J=8.0 Hz, 2H); 13 C NMR (125 MHz,

CDCl 3, ppm) δ 140.0, 136.5, 131.4, 125.3, 125.0, 123.0, 122.8, 122.1, 120.7 (q), 24.5 (q);

19 F NMR (400 MHz, CDCl 3, ppm) δ −68.2

2-Deutero-(benzo[b]thiophene) (225i)

Sodium hydride (0.6 g, 27 mmol) and excess of deuterated dimethylsulfoxide, (CD 3)2SO,

(10mL) were stirred at room temperature for 5 min. Benzothiophene (3.55 g, 27 mmol) was added to the reaction mixture and stirred for 3 h at room temperature. The reaction mixture was first filtered through Kim Wipes, dry Et 2O was added to the filtrate, and

filtered one more time. The filtrate was washed with water and ether. The organic phase 210

was separated, and solvent removed under reduced pressure. A yellowish solid (1.98 g,

56 %) crude product 225i was recovered. MS (EI) m/z: 135(M +); 1H NMR (400 MHz,

DMSO, ppm) δ 8.02-7.97 (d, 1H), 7.91-7.86 (d, 1H), 7.45 (s, 1H), 7.40−7.33 ( m, 2H).

2-Deutero 3-bromo-(benzo[b]thiophene) (226i)

Deutero benzothiophene 225i (1.9 g, 14 mmol ) was dissolved in CCl 4 (75 mL) and stirred at 0 °C for 5 min. Bromine (0.71 mL, 14 mmol ) was added all at once and stirred at 0 °C. The reaction mixture was stirred at room temperature for 2 days. The reaction mixture was washed with H 2O and saturated Na 2CO 3. The organic phase was separated, dried over Na 2SO 4 and solvent removed under reduced pressure. Crude product 226i

(2.95 g, 98 %) was recovered. MS (EI) m/z: 213(M +), 215 (M2+); 1H NMR (400 MHz,

DMSO, ppm) δ 8.08-8.04 (d, 1H), 7.78-7.74 (d, 1H), 7.55−7.45 ( m, 2H).

2-Deutero-1-(benzo[b]thiophen-3-yl)-2, 2, 2-trifluoroethanone (227i)

2-Deutero 3-bromo-(benzo[b]thiophene) (226i) (2.95 g, 14.0 mmol) was dissolved in dry

Et 2O (125 mL) and stirred at -70 °C (ethanol and liquid nitrogen bath) under argon

atmosphere. t-BuLi (18.0 mL, 30 mmol, 1.7M pentane) was added dropwise (15 min)

stirring the reaction mixture at -70 °C . The reaction mixture was stirred at -70 °C for 30 min. CuBr(Me) 2S (3.0 g, 15 mmol) was added at one portion keeping the reaction mixture at -70 °C . The reaction mixture was stirred for 10 min and trifluoroacetic anhydride (TFAA), (2.0 mL, 14 mmol) was added dropwise at -35 °C. The reaction

mixture was stirred at -20 °C for 8 h. Saturated NH 4Cl (2 g, 50 mL) was added dropwise at -70 °C and left stirring while the cold bath naturally warmed for 8 h. The temperature 211

of the cold bath after 8 h was +12 °C. The reaction mixture was brought to room temperature and washed with ether and water. The organic phase was separated, dried over MgSO 4, and solvent condensed under reduced pressure. Liquid crude product 227i

1 (2.35 g, 42 %) was obtained. H NMR (400 MHz, CDCl 3, ppm) δ 8.72-8.72 (d, 1H),

7.94-7.90 (d, 1H), 7.60-7.55 (dd, 1H), 7.53− 7.48(dd, 1H).

2-Deutero-1-(benzo[b]thiophen-3-yl)-2, 2, 2-trifluoroethanone oxime (228i)

Crude ketone 227i (0.15 g, 0.7 mmol) was dissolved in ethanol (5 mL), pyridine (5 mL)

was added and the reaction mixture was stirred at room temperature for 5 min.

NH 2OH.HCl (0.14g, 2 mmol) was added at one portion to the reaction mixture and

refluxed for 15 h under nitrogen atmosphere. The reaction mixture was allowed to come

to room temperature and concentrated under reduced pressure to remove pyridine. The

condensed product was dissolved in dichloromethane and washed with saturated citric

acid. The organic phase was separated, dried over anhydrous MgSO 4, and condensed

under reduced pressure. Crude product 228i (0.15 g, 85 %) as a mixture of syn and anti isomer was recovered, which was used for the next step without further purification.

1 H NMR (400 MHz, CDCl 3, ppm) δ 8.61-8.57 (s, 1H), 8.44-8.40 (s, 1H), 8.06-8.01 (d,

1H), 7.95-7.85 (m, 2H), 7.65-7.61 (m, 1H), 7.47− 7.38( m, 4H).

2-Deutero-1-(benzo[b]thiophen-3-yl)-2, 2, 2-trifluoroethanone O-tosyloxime (229i) 212

Crude oxime 228i (0.2 g, 0.8 mmol) was dissolved in CH 2Cl 2 (10 mL). Et 3N (0.4 mL, 2.4 mmol) and a catalytic amount of dimethylaminopyridine (DMAP) were added and stirred in an ice-chilled water bath for 5 min. p-TsCl ( 0.16 g, 0.8 mmol ) was added portionwise

(5 min) and stirred in an ice-chilled water bath for 12 h. The mixture was washed with water and CH 2Cl 2. The organic phase was separated, dried over anhydrous MgSO 4, and condensed under reduced pressure. Crude product 229i (0.30 g, 93 %) was recovered. 1H

NMR (400 MHz, CDCl 3, ppm) δ 7.92-7.86 (m, 3 H), 7.47-7.38(m, 4 H), 7.36-7.32(d, 1

19 H), 2.52−2.49 (s, 3 H). F NMR (CDCl 3) δ -68.1.

2-Deutero-3-(benzo[b]thiophen-3-yl)-3-(trifluoromethyl)-3-H-diaziridine (230i)

Crude tosyl oxime 229i (0.3 g, 0.8 mmol) was dissolved in CH 2Cl 2 (10 mL). The reaction

o mixture was stirred at -60 C (ethanol and liquid nitrogen) and ammonia gas (NH3) was added and condensed to liquid ammonia, approximately 50 mL. The reaction mixture was stirred for 18 h at -60 o C. The cold bath was removed and left at room temperature to

allow NH 3 to evaporate, for 5 h The reaction mixture was washed with water (25 mL) and CH 2Cl 2 ( 35 mL). The organic phase was separated, dried over Na 2SO 4, and solvent

was removed under reduced pressure. After column chromatography (1: 29 EtOAc:

1 Hexane) diaziridine 230i (0.1 g, 32 %) was recovered. H NMR (400 MHz, CDCl 3, ppm)

δ 8.03-7.96 (d, 1H), 7.92-7.86 (d, 1H), 7.48-7.38 (ddd, 2H), 2.90-2.80 (d, 1H),

2.45−2.35 ( d, 1H);

2-deutero-3-(benzo[b]thiophen-3-yl)-3-(trifluoromethyl)-3-H-diazirine (223i) 213

Diaziridine 230i (0.2 g, 0.8 mmol) was dissolved in CH 2Cl 2 (4 mL) and stirred at 0 °C.

Et 3N (0.6 mL, 1.6 mmol) was added and the reaction mixture was stirred for 5 min.

Iodine (0.2 g, 0.8 mmol) was added portion wise (3 min) and the reaction mixture stirred

for 1 h at 0 °C. The reaction mixture was washed with sodium hydroxide solution (15mL)

and CH 2Cl 2 (40mL). The organic phase was separated, dried over Na 2SO 4, and solvent

removed under reduced pressure. Column chromatography (hexane) yielded (0.12 g, 63

1 %) diazirine 223i. H NMR (400 MHz, CDCl 3, ppm) δ 7.50−7.40( m, 2H), 7.90-7.85 (d,

19 1H), 8.12-8.08 (d, 1H); F NMR (376 MHz, CDCl 3, ppm) δ −67.8

N-Methyl- Indole (238) 124,125

Indole (237) (5.0 g, 43 mmol) was dissolved in acetone (100 mL) and stirred at room temperature for 10 min. KOH (11.97 g, 213 mmol) was added to the reaction mixture at

0 °C and stirred for 30 min. The cold bath was removed and the reaction mixture stirred

at room temperature for 24 h. The reaction mixture was washed with water and extracted

with ether. Solvent was removed under reduced pressure and the concentrated liquid was

purified via distillation under vacuum. Liquid N-methyl indole (4 g, 71 %) was obtained

1 124 1 after distillation. H NMR matched the literature values. H NMR (400 MHz, CDCl 3,

ppm) δ 7.63 (d, J = 7.9 Hz, 1H), 7.31 (d, J = 8.0 Hz, 1H), 7.29 – 7.15 (m, 1H), 7.10 (m,

1H), 7.04 (d, J = 3.1 Hz, 1H), 6.48 (d, J = 3.1, Hz, 1H), 3.78 (s, 3H).

2, 2, 2-Trifluoro-1-(1-methyl-1H-indol-2-yl)ethanone (240) 214

N-Methyl indole (238) (5.4 g, 41 mmol) was dissolved in anhydrous ether (60 mL) and stirred at -60 °C for 10 min. t-BuLi (24 mL, 41 mmol) was added dropwise (10 min) to

the reaction mixture. The cold bath was removed and reaction mixture was stirred at

room temperature for 1 h. The reaction mixture was cooled at -50 °C and 1- trifluoroacetyl piperidine (239) (10.0 g, 55 mmol), dissolved in anhydrous ether (20mL)

was added dropwise (15 min) from -50 °C to -35 °C . The reaction mixture was stirred for

15 min at -35 °C and the cold bath was removed and the reaction mixture was stirred at room temperature for 80 min. The reaction mixture was cooled to -80 °C and saturated

NH 4Cl was added dropwise (10 min). The mixture was washed with water and brine. The

organic phase was separated, dried over anhydrous MgSO 4, and concentrated in vacuum.

Crude ketone 240 (5.6 g, 61 %) was recovered. MS (EI) m/z: 227 (M +); mp 104-105 °C ;

1 H NMR (400 MHz, CDCl 3, ppm) δ δ 7.77-7.73 (d, J=8.2 Hz, 1H), 7.60-7.57 (s, 1H),

7.60-7.57 (s, 1H), 7.51-7.40 (m, 2H), 7.23-7.18 (m, 1H), 4.11 (s, 3H); 19 F NMR (376

13 MHz, CDCl 3, ppm) δ -72.3; C NMR (125 MHz, CDCl 3, ppm) δ 172.1 ( q ), 140.39,

127.27, 127.12, 124.91, 123.0, 120.67, 115.62 (q), 112.2 (q), 109.51, 31.35.

2, 2, 2-Trifluoro-1-(1-methyl-1H-indol-2-yl)ethanone oxime (241)

Crude ketone 240 (4.40g, 19 mmol) was dissolved in EtOH (25 mL) and pyridine (20

mL) was added and the reaction mixture was stirred at room temperature for 5 min.

NH 2OH.HCl (0.86 g, 12 mmol) was added in one portion to the reaction mixture and

refluxed at 90 °C for 39 h under nitrogen atmosphere. The reaction mixture was allowed to come to room temperature and concentrated under reduced pressure to remove 215

pyridine. The remaining pyridine was removed with mechanical vacuum pump over 24 h.

The concentrated product was dissolved in CH 2Cl 2 (25mL) and washed with water. The

organic phase was separated, dried over anhydrous MgSO 4 and solvent removed under reduced pressure. Crude liquid product 241 (4.0 g, 85 %) was recovered. MS (EI) m/z:

+ 1 242(M ); H NMR (500 MHz, CDCl 3, ppm) δ 9.43 (s, 1H), 7.94 – 7.62 (m, 2H), 7.52 –

19 13 7.02 (m, 3H), 3.85 (s, 3H); F NMR (376 MHz, CDCl 3, ppm) δ -65.3; C NMR (125

MHz, CDCl 3, ppm) δ 142.97 (q), 136.55, 133.00, 125.61, 122.81, 122.35, 121.09, 120.33

(q), 118.11, 100.74, 33.39.

2, 2, 2-Trifluoro-1-(1-methyl-1H-indol-2-yl)ethanone O-mesyl oxime (242)

Crude oxime 241 (4.0 g, 16.5 mmol,) was dissolved in anhydrous tetrahydrofuran (THF)

(30 mL) and stirred for 5 min at 0 °C. Mesyl chloride (2.54 mL, 33.0 mmol) was added dropwise to the reaction mixture, followed by dropwise addition of triethylamine (34.55 mL, 3 mmol) at 0 °C. The reaction mixture was stirred for 3.5 h at room temperature. The solvent was removed under reduced pressure and the obtained product was dissolved in dichloromethane and washed with water. The separated organic phase was dried over anhydrous magnesium sulfate, and condensed under reduced pressure. The obtained product was recrystallized in ether and hexane, and pure mesyl oxime 242 (1.75g, 33 %)

1 was recovered. H NMR (400 MHz, CDCl 3, ppm) δ 7.71−7.67 ( d, J=8.0

Hz , 1Η), 7.69 ( s, 1Η), 7.41−7.38 ( m, 2Η), 7.18−7.12 ( m, 1Η), 3 .72 ( s, 3Η), 3.27 ( s, 3Η)

2, 2, 2-Trifluoro-1-(1-methyl-1H-indol-2-yl)ethanone O-tosyl oxime 216

Crude oxime 241 (1.4 g, 5.7 mmol) was dissolved in CH 2Cl 2 (10 mL). Et 3N (1.0 mL, 7.22

mmol) and a catalytic amount of DMAP were added and stirred at 0 °C for 5 min. p-

TsCl (1.04 g, 5.7 mmol ) was added portionwise (5 min) and stirred at 0 °C for 12 h.

The mixture was washed with water and CH 2Cl 2. The organic phase was separated, dried over anhydrous Na 2SO 4, and condensed under reduced pressure. Crude product as a yellowish solid (1.87 g, 82 %) was recovered. mp 122-133 °C ; 1H NMR (400 MHz,

CDCl 3, ppm) δ 7.97 – 7.89 (m, 2H), 7.72 – 7.60 (m, 2H), 7.40 – 7.19 (m, 5H), 3.88 –

19 13 3.68 (m, 3H), 2.43 (s, 3H); F NMR (376 MHz, CDCl 3, ppm) δ -66.12; C NMR

(125 MHz, CDCl 3, ppm) δ 148.74 (q), 145.87, 136.67, 134.42 (q), 131.56, 129.75,

129.25, 125.39, 123.31, 122.09, 121.95, 119.39 (q), 110.08, 99.84, 33.92, 22.08.

1-Methyl-2-(3-trifluoromethyl)diaziridin-3-yl)-1H-indole (243)

Mesyl oxime 242 (1.75g, 5.5 mmol) was dissolved in CH 2Cl 2 (15 mL). The reaction

o mixture was stirred at -78 C (ethanol and liquid nitrogen) and ammonia gas (NH3) was added and condensed to liquid ammonia, approximately 25 mL. The reaction mixture was stirred for 8 h at -78 o C. The cold bath was removed and left at room temperature to allow

NH 3 to evaporate, for 4 h. The reaction mixture was washed with water (50 mL) and

CH 2Cl 2 (50 mL). The organic phase was separated, dried over Na 2SO 4, and solvent was removed under reduced pressure. The obtained product was purified via silica gel column chromatography (1: 4 EtOAc: Hexane), and pure yellow solid diaziridine 243 (0.75 g, 57

+ 1 %) was recovered. MS (EI) m/z: 241(M ); mp 120-135 °C ; H NMR (400 MHz, CDCl 3,

ppm) 7.65-7.61 (d, J = 8.0 Hz, 1H), 7.39-7.29 (M,2H), 7.19-7.13 (m, 1H), 6.77-6.75 217

(s,1H), 3.87-3.85 (s,3H), 2.92-2.86 (d, J = 9.0 Hz, 1H), 2.52-2.46 (d, J = 9.0 Hz, 1H); 19 F

13 NMR (376 MHz, CDCl 3, ppm) δ -76.28; C NMR (125 MHz, CDCl 3, ppm) δ

137.72, 129.94, 126.62, 123.37, 121.94 (q), 121.34, 120.35, 109.64, 104.97, 52.81 (q),

30.98,

1-Methyl-2-(3-trifluoromethyl)-3H-diazirin-3-yl)-1H-indole (244)

Diaziridine 243 (0.06 g, 0.25 mmol) was dissolved in CH 2Cl 2 (10 mL) and stirred -45 °C

(liquid nitrogen and ethanol) under nitrogen. Et 3N (0.15 mL, 1.0 mmol) was added to the

reaction mixture at -45 °C along with iodine (0.08 g, 0.32 mmol), portion wise (3 min)

and the reaction mixture stirred for 15 min at -45 °C . The reaction mixture was washed

with sodium hydroxide solution (10mL) and CH 2Cl 2 (20mL). The organic phase was

separated, dried over Na 2SO 4 and transferred into the deposition tube for low temperature vacuum distillation. The solvent was removed at -25 °C (liquid nitrogen and ethanol)

1 using mechanical pump. H NMR (400 MHz, CDCl 3, ppm) δ 7.60 (d, J = 8.1Hz, 1H),

7.47 – 7.25 (m, 2H), 7.16 – 7.11 (m, 1H) , 6.85 (d, J = 0.8 Hz, 1H), 3.95 (s, 3H); 19 F

NMR (376 MHz, CDCl 3, ppm) δ -68.22.

2, 2, 2-Trifluoro-1-(1H-indol-3-yl)ethanone (250) 124,126-128

Trifluoroacetic anhydride (19 mL, 126.6 mmol) was dissolved in ether (125 mL) and placed in a500 mL round bottom flask. Indole (237) (6.75 g, 57.6 mmol) was dissolved in

ether (25 mL) and added dropwise at -10 °C. The reaction mixture was stirred with

mechanical stirrer for 8 hours at -10 °C. The reaction mixture was quenched with saturated sodium bicarbonate (100 mL) and stirred for 1 h. The organic phase was 218

separated, dried over anhydrous Na 2SO 4, and condensed under reduced pressure. The obtained solid was recrystallized in ethanol. Pure ketone 250 (11.35 g, 92 %) was

126 1 recovered. H NMR (500 MHz, CDCl 3, ppm) δ 12.66 (s, 1H), 8.46 (m, 1H), 8.21 –

13 8.13 (m, 1H), 7.57 (m, 1H), 7.32 (m, 2H); C NMR (125 MHz, CDCl 3, ppm) δ 174.45

(q), 138.07 (q), 137.17, 126.16, 124.92, 123.87, 121.58, 116.10 (q), 113.46, 109.23.

2, 2, 2-Trifluoro-1-(1-methyl-1H-indol-3-yl)ethanone (254)

Ketone 250 (5.0 g, 23.4 mmol) was dissolved in acetone (50 mL) and stirred at room temperature. Potassium carbonate (6.5 g, 46.1 mmol) and methyl iodide (5.84 mL, 93 mmol) were added to the reaction mixture and stirred at room temperature for 6 h. The reaction mixture was washed with water and extracted with dichloromethane. The organic phase was separated, dried over anhydrous MgSO 4, and removed under reduced pressure. White solid ketone 254 (4.75 g, 89 %) was recovered. MS (EI) m/z: 227(M +);

1 mp 104-106 °C ; H NMR (400 MHz, CDCl 3, ppm) δ 8.45 – 8.37 (m, 1H), 7.90 (q, J =

19 1.7 Hz, 1H), 7.44 – 7.36 (m, 3H), 3.91 (s, 3H); F NMR (376 MHz, CDCl 3, ppm) δ -

13 72.29; C NMR (125 MHz, CDCl 3, ppm) δ 172.05 (q), 140.75, 127.63, 127.12, 125.06,

123.42, 120.78, 115.86 (q), 114.51 (q), 109.59, 31.27.

2, 2, 2-Trifluoro-1-(1-methyl-1H-indol-3-yl)ethanone oxime (255)

Ketone 254 (4.56 g, 19.9 mmol) was dissolved in ethanol (20 mL). Hydroxylamine

hydroc hloride (13.88 g, 199 mmol) and pyridine (20 mL) was added to the reaction

mixture and refluxed for 50 h. Pyridine was removed under reduced pressure and the

reaction mixture washed with 1M HCl and extracted with dichloromethane. The organic 219

phase was separated, dried over anhydrous MgSO 4, and solvent removed under reduced

pressure. The obtained crude product was recrystallized in chloroform and solid oxime

255 (3.90 g, 80 %) was obtained. MS (EI) m/z: 242(M +); mp 150-152 °C ; 1H NMR (400

MHz, CDCl 3, ppm) δ 9.16 (d, J = 1.6 Hz, 1H), 7.83 – 7.62 (m, 3H), 7.44 – 7.11 (m, 6H),

19 13 3.85 (q, J = 1.1 Hz, 5H); F NMR (376 MHz, CDCl 3, ppm) δ −66.21; C NMR (125

MHz, CDCl 3, ppm) δ 142.99 (q), 136.55, 132.74, 125.68, 122.80, 122.4 (q), 121.04,

120.27 (q), 109.75, 100.77, 33.36.

2, 2, 2-Trifluoro-1-(1-methyl-1H-indol-3-yl)ethanone O-mesyl oxime (257)

Oxime 255 (2.75 g, 11.3 mmol) was dissolved in anhydrous tetrahydrofuran (THF) (30 mL) and stirred for 5 min at 0 °C. Mesyl chloride (2.0 mL, 25.8 mmol) was added dropwise to the reaction mixture, followed by dropwise addition of triethylamine (3 mL,

21.6 mmol). The reaction mixture was stirred for 4 h at room temperature. The solvent was removed under reduced pressure and the obtained product was dissolved in dichloromethane and washed with water. The organic phase was separated, dried over anhydrous magnesium sulfate, and removed under reduced pressure. The obtained product was recrystallized in chloroform and a yellowish solid, mesyl oxime 257 (2.5g,

1 71 %) was obtained. mp 99-131 °C ; H NMR (400 MHz, CDCl 3, ppm) d 7.81 (d, J =

0.9 Hz, 1H), 7.76 (d, J = 8.0 Hz, 1H), 7.44 – 7.26 (m, 3H), 3.88 (s, 3H), 3.27 (s, 3H); 19 F

13 (376 MHz, CDCl 3, ppm) δ −65.19; C NMR (125 MHz, CDCl 3, ppm) δ 149.31 (q),

136.74, 135.03 (q), 125.33, 123.50, 122.26 (q), 121.59 (q), 110.13, 99.75, 33.66, 31.53.

2, 2, 2-Trifluoro-1-(1-methyl-1H-indol-3-yl)ethanone O-tosyl oxime (256) 220

Oxime 255 (5.0 g, 20.6 mmol) was dissolved in dichloromethane (30 mL) and stirred at

room temperature until the oxime was completely dissolved. Triethylamine (3.2 mL, 23.1

mmol) was added to the reaction mixture and stirred at room temperature for 3 min.

Dimethylaminopyridine (0.02 g, 0.1 mmol) was added to the reaction mixture along with

tosylchloride (3.89 g, 20.4 mmol) and the reaction mixture was stirred at 0 °C for 5 min.

The reaction mixture was stirred at room temperature for 48 h. The reaction mixture was

washed with water. The organic phase was separated, dried over anhydrous magnesium

sulfate, and solvent removed under reduced pressure. Yellow solid, tosyl oxime 256

1 (8.03 g , 99 %) was recovered. mp 133-137 °C ; H NMR (400 MHz, CDCl 3, ppm)

δ 7.98 – 7.88 (d, 8.0 Hz, 2H), 7.73 (s, 1H), 7.72 – 7.59 (m, 1H), 7.43 – 7.20 (m, 5H),

19 13 3.86 (s, 3H), 2.46 (s, 3H); F NMR (376 MHz, CDCl 3, ppm) δ −65.54; C NMR (125

MHz, CDCl 3, ppm) δ 148.71(q), 145.76, 136.65, 134.47 (q), 131.59, 129.72, 129.31,

125.38, 123.33, 122.16 (q), 122.00 , 119.35 (q) , 109.99, 99.94, 33.60, 21.76.

1-Methyl-3-(3-trifluoromethyl)diazirdin-3-yl)-1H-indole (258)

Mesyl oxime 257 (0.8 g, 2.6 mmol) was dissolved in CH 2Cl 2 (10 mL). The reaction

o mixture was cooled at -78 C (ethanol and liquid nitrogen) and ammonia gas (NH3) was added and condensed to liquid ammonia (25 mL), approximately. The reaction mixture was stirred for 36 h at -78 o C. The cold bath was removed and left at room temperature to

allow NH 3 to evaporate, for 5 h. The reaction mixture was washed with water (50 mL)

and CH 2Cl 2 (50 mL). The organic phase was separated, dried over Na 2SO 4, and removed

under reduced pressure. Even after several attempts of purification via silica gel column 221

chromatography only liquid crude diaziridine 258 (0.2g, 34 %) was recovered. 1H NMR

(400 MHz, CDCl 3, ppm) δ 7.82 (d, J = 7.9 Hz, 1H), 7.43 – 7.25 (m, 3H), 7.19 (dd, J =

8.2, 6.8 Hz, 1H), 3.81 (s, 3H), 2.76 (d, J = 9.0 Hz, 1H), 2.26 (d, J = 9.0 Hz, 1H); 19 F

NMR (376 MHz, CDCl 3, ppm) δ−65.19.

1-Methyl-3-(3-trifluoromethyl)diazirin-3-yl)-1H-indole (259)

Diaziridine 258 (0.08g, 0.33 mmol) was dissolved in dichloromethane (10 mL) and

stirred at -10 °C (cold bath, liquid nitrogen and ethanol) under nitrogen. Triethylamine

(1.0 mmol, 0.15 mL) was added to the reaction mixture at -10 °C. Iodine (0.08 g, 0.32

mmol) was added in one portion and the reaction mixture was stirred for 15 min at -10 °C

to O °C. The work up was done with sodium hydroxide solution (10 mL). The oxidation reaction and work-up was done within 2-20 min. We were never able to get a clean NMR of diazirine 259 because of instability. The organic phase was separated and directly

transferred into the deposition tube for low temperature vacuum distillation. The solvent

was removed at -25 °C (liquid nitrogen and ethanol) using a mechanical pump

1-(Benzo[d]thiazol-2-yl)-2, 2, 2-trifluorothanone (273) 130

Benzothiazole (270) ( 2.64 g, 19.5 mmol) was dissolved in toluene (70 mL) and stirred at

-35 °C (ethanol and liquid nitrogen). TFAA (4.4 mL, 21 mmol) was added dropwise (45

min) and stirred for 30 min at -35 °C. Et 3N (3.0 mL, 21 mmol) was added dropwise at -

35°C. The reaction mixture was stirred for 6 h at -19 °C and stirred overnight at room temperature. The reaction mixture was condensed under reduced pressure and mechanical vacuum pump for 48 h. Mixture of green solid and liquid was obtained. The NMR of the 222

green solid (3.5 g, 73%) matched the literature NMR of 273 .130 1H NMR (400 MHz,

CDCl 3, ppm) δ 8.34 (d, J=7.2 Hz, 1H), 8.05 (d, J=8.4 Hz, 1H), 7.66 (m, 2H).

1-(Benzo[d]thiazol-2-yl)-2, 2, 2-trifluorothanone oxime (274)

Crude ketone 273 (1.03 g, 4.4 mmol) was dissolved in toluene (50 mL). NH 2OH.HCl

(0.62 g, 8.9 mmol) was added in the reaction mixture along with catalytic amount of p-

toluene sulfonic acid and refluxed using a Dean Stark distillation apparatus for 30 min.

The viscous liquid collected in the Dean Stark apparatus was discarded and the reaction

mixture was concentrated in vacuuo. The concentrated reaction mixture was dissolved in

CH 2Cl 2 and washed with water. The separated organic phase was dried over Na 2SO 4, and

solvent was removed under reduced pressure. A viscous liquid was obtained which

solidified at room temperature and oxime 274 (0.25 g, 23 %) was obtained. The liquid containing impure oxime 274 was discarded. MS (EI) m/z: 246(M +); mp 181-186 °C ; 1H

NMR (400 MHz, CDCl 3, ppm) δ 9.08 (s, 1H), 8.23 – 8.14 (m, 1H), 8.09 – 7.98 (m, 1H),

19 13 7.75 – 7.57 (m, 2H); F NMR (376 MHz, CDCl 3, ppm) δ −65.28; C NMR (125

MHz, CDCl 3, ppm) δ 152.84, 150.15, 138.67 (q), 13 4.09, 127.78, 127.62, 123.92,

121.65, 119.45 .

1-(Benzo[d]thiazol-2-yl)-2, 2, 2-trifluorothanone tosyl oxime (275)

Crude oxime 274 (1.4 g, 5.6 mmol) was dissolved in CH 2Cl 2 (10 mL). A catalytic amount

of DMAP along with Et 3N (1.0 mL, 7.2 mmol) were added to the reaction mixture and stirred at room temperature for 15 min. p-TsCl (1.04 g, 5.6 mmol) was added portion wise (10 min) keeping the reaction mixture at 0 °C. The reaction mixture was stirred 223

overnight at room temperature and washed with water. The organic phase was separated, dried over anhydrous sodium sulfate and removed under reduced pressure. Yellowish solid tosyl oxime 275 (1.87 g, 82 %) was recovered. For characterization purpose, a

portion of product was recrystallized in ether and hexane. mp 135-151 °C ; 1H NMR

(400 MHz, CDCl 3, ppm) δ 8.42 – 8.13 (m, 1H), 8.18 – 7.83 (m, 3H), 7.80 – 7.55 (m, 2H),

19 13 7.42 (d, J = 8.2 Hz, 2H), 2.48 (s, 3H); F NMR(376 MHz, CDCl 3, ppm) δ −64.52; C

NMR (125 MHz, CDCl 3, ppm) δ 151.38, 148.56 (q), 146.84, 146.54 (q), 138.79, 136.60,

130.59, 130.12, 129.48, 128.27, 127.51, 125.68, 121.49, 118.20 (q), 21.85.

2-(3-(Trifluoromethyl)diaziridin-3-yl)benzo[d]thiazole (276)

Tosyl oxime 276 (1.87 g, 4.6 mmol) was dissolved in CH 2Cl 2 (15 mL) and cooled to -78

°C. Liquid ammonia (ca. 50 mL), was condensed into the reaction flask. The reaction mixture was stirred for 5 h at -60 °C and left to warm up to room temperature to evaporate

the ammonia. The reaction mixture was washed with water and extracted with CH 2Cl 2.

The organic phase was separated, dried over anhydrous sodium sulfate and condensed

under reduced pressure. Solid diaziridine 276 (0.85 g, 75 %) was obtained. 1H NMR

(400 MHz, CDCl 3, ppm) δ 8.30 – 8.03 (m, 1H), 7.92 (m, 1H), 7.78 – 7.39 (m, 2H), 3.40 –

19 13 2.98 (m, 2H); F NMR (376 MHz, CDCl 3, ppm) δ−74.29; C NMR (100 MHz,

CDCl 3, ppm) δ 161.05, 152.63, 135.09, 126.79, 126.51, 124.04, 121.77, 121.02 (q),

56.09 (q).

2-(3-(Trifluoromethyl)-3H-diazirin-3-yl)benzo[d]thiazole (277) 224

Diaziridine 276 (0.15 g, 0. 6 mmol) was dissolved in methanol (10 mL) and Et 3N (0.16

mL, 1.2 mmol) was added and stirred at 0 °C. Iodine (0.15 g, 0.6 mmol) was added

portion wise (5 min) and stirred for 1.5 h at 0 °C. The reaction mixture was washed with

sodium hydroxide solution (10 mL) and extracted with CH 2Cl 2. The organic phase was

separated, dried over Na 2SO 4, and condensed under reduced pressure. Yellow solid

1 diazirine 277 (0.12 g, 82 %) was recovered. H NMR (400 MHz, CDCl 3, ppm) δ 8.08 (d,

19 J = 8.1 Hz, 1H), 7.91 (d, J = 7.9 Hz, 1H), 7.52 (m, 2H); F NMR (376 MHz, CDCl 3,

13 ppm) δ -65.94; C NMR (125 MHz, CDCl 3, ppm) δ 158.36, 152.80, 134.56, 127.09,

126.52, 124.02, 121.53, 119.91 (q), 29.31 (q) .

1-(Benzo[d]oxazol-2-yl)-2, 2, 2-trifluorothanone (284) 130

Benzoxazole (283) (14.75 g, 124 mmol) was dissolved in toluene (100 mL) and stirred at

-20 °C. TFAA (21 mL, 149 mmol) was added dropwise (30 min) and stirred at -20 °C for

30 min. Et 3N (20.5 mL, 149 mmol) was added dropwise (15 min) at -20 °C and stirred for 10 hr. The reaction mixture was concentrated under reduced pressure in a water bath temperature around 40 °C. The condensed liquid was left at room temperature which

solidified into crystals. The crystals were separated from the mother liquor. A yield was

not calculated as the product contains Et 3N salt, and aqueous workup was not attempted because ketone readily makes hydrates. The obtained crude ketone 1H NMR matched the

130 1 literature values. H NMR (400 MHz, CDCl 3, ppm) δ 8.03 (d, J = 8.1, Hz, 1H), 7.73

(d, J = 8.4 Hz, 1H), 7.66 (m, 1H), 7.56 (m, 1H).

1-(Benzo[d]oxazol-2-yl)-2, 2, 2-trifluorothanone oxime (285) 225

Crude ketone 284 (2.0 g, 9 mmol) was dissolved in toluene (50 mL). NH 2OH.HCl (1.3 g,

18 mmol) was added in the reaction mixture along with catalytic amount of p-toluene

sulfonic acid and refluxed using a Dean Stark distillation apparatus for 30 min. The

viscous liquid collected in the Dean Stark apparatus was discarded and the reaction

mixture was concentrated in vacuuo. The concentrated reaction mixture was dissolved in

CH 2Cl 2 and washed with water. The separated organic phase was dried over Na 2SO 4, and

solvent removed under reduced pressure. A viscous liquid was obtained which solidified

at room temperature and oxime 285 (1.65 g, 80 %) was obtained. 1H NMR (400 MHz,

19 CDCl 3, ppm) δ 7.87 (d J = 8.0 Hz, 1H), 7.74 (d J = 8.2 Hz, 1H), 7.68 – 7.48 (m, 2H); F

NMR (376 MHz, CDCl 3, ppm) δ−65.15 .

1-(Benzo[d]oxazol-2-yl)-2, 2, 2-trifluorothanone O- tosyl oxime (285)

Crude oxime 284 (1.0 g, 4.3 mmol) was dissolved in CH 2Cl 2 (25 mL). A catalytic

amount of DMAP along with Et 3N (0.6 mL, 4.3 mmol) were added to the reaction mixture and stirred at room temperature for 15 min. p-TsCl (0.8 g, 4.3 mmol) was added portion wise (10 min) keeping the reaction mixture at 0 °C. The reaction mixture was stirred overnight at room temperature and washed with water. The organic phase was separated, dried over anhydrous sodium sulfate and removed under reduced pressure.

White solid tosyl oxime 285 (1.5 g, 87 %) was recovered. mp 97-102 °C ; 1H NMR (400

MHz, CDCl 3, ppm) δ 8.02 – 7.95 (m, 2H), 7.93 (d, J = 8.1 Hz, 1H), 7.71 (d, J = 8.3 Hz,

1H), 7.57 (dd, J = 8.4, 7.3, Hz, 1H), 7.49 (dd, J = 8.2, 7.5, Hz, 1H), 7.43 – 7.37 (m, 2H),

19 13 2.49 (s, 3H); F NMR (376 MHz, CDCl 3, ppm) δ −65.49; C NMR (125 MHz, 226

CDCl 3, ppm) δ 150.27, 148.51, 146.70, 140.15, 130.53, 130.03, 129.51, 128.71, 126.09,

122.19, 117.75 (q), 111.76, 21.79.

2-(3-(Trifluoromethyl)diaziridin-3-yl)benzo[d]oxazole (286)

Tosyl oxime 285 (1.5 g, 3.7 mmol) was dissolved in CH 2Cl 2 (10 mL) and cooled to -78

°C. Liquid ammonia (ca. 50 mL) was condensed into the reaction flask. The reaction mixture was stirred for 5 h at -78 °C and left to warm up to room temperature for 5 h to evaporate the ammonia. The reaction mixture was washed with water and extracted with

CH 2Cl 2. The organic phase was separated, dried over anhydrous sodium sulfate and

condensed under reduced pressure. Solid diaziridine 286 (0.6 g, 71 %) was obtained. 1H

NMR (400 MHz, CDCl 3, ppm) δ 7.84 – 7.78 (m, 1H), 7.66 – 7.58 (m, 1H), 7.50 – 7.38

19 (m, 2H), 3.32 (d, J = 9.4 Hz, 1H), 3.02 (d, J = 9.5 Hz, 1H); F NMR (376 MHz, CDCl 3,

ppm) δ −74.76.

2-(3-(Trifluoromethyl)-3H-diazirin-3-yl)benzo[d]oxazole (287)

Diaziridine 286 (0.09 g, 0. 04 mmol) was dissolved in methanol (10 mL) and Et 3N (0.12

mL, 0.86 mmol) was added and stirred at 0 °C. Iodine (0.1 g, 0.04 mmol) was added

portion wise (5 min) and stirred for 1.5 h at 0 °C. The work up was done with sodium

hydroxide solution (10 mL) and extracted with CH 2Cl 2. The organic phase was separated, dried over Na 2SO 4, and condensed under reduced pressure. Yellow solid, diazirine 287

1 (0.06 g, 66 %) was recovered. H NMR (400 MHz, CDCl 3, ppm) δ 7.80 – 7.69 (m, 1H),

19 7.60 – 7.51 (m, 1H), 7.47 – 7.34 (m, 2H), 5.30 (s, 1H); F NMR (376 MHz, CDCl 3, 227

13 ppm) δ -66.09; C NMR (125 MHz, CDCl 3, ppm) δ 154.92, 150.79, 140.32, 126.59,

125.59, 120.73, 119.30 (q), 110.96, 25.05 (q).

References

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231

B3LYP 6-31+G** level

3-Benozthienyl(CF 3)diazirine (223)

Standard orientation: ------Center Atomic Atomic Coordinates Number Number Type X Y Z ------1 6 0 -2.460417 -2.272081 -0.080223 2 6 0 -3.591263 -1.456398 -0.276983 3 6 0 -3.478969 -0.069475 -0.269152 4 6 0 -2.214458 0.492310 -0.058090 5 6 0 -1.065454 -0.312124 0.142258 6 6 0 -1.205362 -1.713790 0.127073 7 16 0 -1.811919 2.202845 -0.011881 8 6 0 -0.137349 1.833516 0.278077 9 6 0 0.123528 0.494244 0.337489 10 6 0 1.479508 -0.056619 0.584779 11 6 0 2.443498 -0.156271 -0.580174 12 9 0 3.613456 -0.722600 -0.214858 13 9 0 2.725757 1.066682 -1.093244 14 9 0 1.922727 -0.897325 -1.585829 15 7 0 2.099722 0.096066 1.927214 16 7 0 1.689156 -1.031908 1.686342 17 1 0 -2.571311 -3.351991 -0.092961 18 1 0 -4.562830 -1.913252 -0.438784 19 1 0 -4.350079 0.559594 -0.423927 20 1 0 -0.338721 -2.350107 0.273381 21 1 0 0.574460 2.640437 0.392552 ------

Zero-point correction= 0.132639 (Hartree/Particle)

Sum of electronic and zero-point Energies= -1191.1294844

TD B3LYP of diazirine 223

Excitation Energies and Oscillation Strengths

Excited State 1: Singlet-A 3.0747 eV 403.24 nm f=0.0071 61 -> 62 0.69941

Excited State 2: Singlet-A 3.6144 eV 343.03 nm f=0.0033 60 -> 62 0.70398 232

Excited State 3: Singlet-A 3.9515 eV 313.76 nm f=0.0006 58 -> 62 0.53845 59 -> 62 -0.40319

Excited State 4: Singlet-A 4.5654 eV 271.57 nm f=0.0697 60 -> 63 -0.26964 60 -> 64 -0.20807 61 -> 63 0.56338 61 -> 64 -0.15023

Excited State 5: Singlet-A 4.7860 eV 259.05 nm f=0.0050 58 -> 62 0.40853 59 -> 62 0.55131 61 -> 63 -0.10769

Excited State 6: Singlet-A 4.8742 eV 254.37 nm f=0.0409 59 -> 62 0.11151 60 -> 63 0.43815 61 -> 63 0.25996 61 -> 64 0.41485 61 -> 66 -0.11309

Excited State 7: Singlet-A 5.1781 eV 239.44 nm f=0.0014 61 -> 65 0.68294

Excited State 8: Singlet-A 5.4114 eV 229.12 nm f=0.1814 59 -> 63 0.17259 60 -> 63 -0.35510 60 -> 64 0.12829 60 -> 66 0.11180 61 -> 64 0.44801 61 -> 66 0.18681

Excited State 9: Singlet-A 5.6786 eV 218.34 nm f=0.0069 60 -> 64 -0.15616 60 -> 65 0.66212

**********************************************************************

233

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Spectrum: B3LYP predicted IR spectra of diazirine 223

3-Benozthienyl(CF 3)carbene 224a singlet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 2.901541 -2.019395 -0.009203 2 6 0 3.822923 -0.955885 0.004689 3 6 0 3.384538 0.366537 0.009050 4 6 0 2.004465 0.588183 -0.002321 5 6 0 1.066310 -0.459732 -0.016985 6 6 0 1.530200 -1.782038 -0.019639 7 16 0 1.179471 2.157075 0.005229 8 6 0 -0.353358 1.427919 -0.022187 9 6 0 -0.329331 0.014043 -0.027552 10 6 0 -1.401998 -0.882684 -0.014781 11 6 0 -2.805227 -0.386199 -0.003657 12 9 0 -3.575616 -1.110364 -0.850674 13 9 0 -3.088504 0.935219 -0.344208 14 9 0 -3.292286 -0.538140 1.257745 15 1 0 3.268600 -3.041264 -0.010992 16 1 0 4.888194 -1.165234 0.012893 234

17 1 0 4.091058 1.190514 0.020923 18 1 0 0.806418 -2.590543 -0.028598 19 1 0 -1.238540 2.048393 -0.028137 ------

Zero-point correction= 0.1218682 (Hartree/Particle)

Sum of electronic and zero-point Energies= -1081.6016883

TD B3LYP of 224a singlet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 1.2131 eV 1022.07 nm f=0.0012 54 -> 55 0.60444 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.9937 eV 414.15 nm f=0.0482 51 -> 55 -0.17433 53 -> 55 0.64732

Excited State 3: Singlet-A 3.1673 eV 391.46 nm f=0.0288 52 -> 55 0.67317

Excited State 4: Singlet-A 3.9370 eV 314.92 nm f=0.0013 54 -> 56 0.69118

Excited State 5: Singlet-A 4.4714 eV 277.28 nm f=0.0003 54 -> 57 0.70298

Excited State 6: Singlet-A 4.6426 eV 267.06 nm f=0.0382 51 -> 55 0.46932 54 -> 58 0.49756

Excited State 7: Singlet-A 5.0397 eV 246.01 nm f=0.0211 52 -> 56 0.41851 52 -> 57 0.19879 53 -> 56 -0.28792 53 -> 57 0.41467 54 -> 58 0.14899

Excited State 8: Singlet-A 5.1164 eV 242.33 nm f=0.2101 51 -> 55 -0.38344 52 -> 56 -0.21056 52 -> 57 0.12158 53 -> 57 -0.12550 54 -> 58 0.44027 235

Excited State 9: Singlet-A 5.2779 eV 234.91 nm f=0.0015 48 -> 55 -0.30066 50 -> 55 0.61884

**********************************************************************

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Spectrum: B3LYP predicted IR spectra of 224a singlet

3-Benozthienyl(CF 3)carbene 224a triplet

10 6 0 -1.451255 -0.588753 -0.060813 11 6 0 -2.893261 -0.349718 0.002912 12 9 0 -3.594076 -1.372433 -0.543472 13 9 0 -3.257137 0.789239 -0.663071 14 9 0 -3.353193 -0.200703 1.279746 15 1 0 3.048930 -3.185465 -0.005821 16 1 0 4.808695 -1.436851 0.033685 17 1 0 4.195707 0.969218 0.040613 18 1 0 0.646838 -2.553075 -0.039636 19 1 0 -1.059557 2.239589 -0.044630 ------

Zero-point correction= 0.121214 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.601601 S2=2.033137\S2-1=0.\S2A=2.000284

TD B3LYP of 224a triplet

Excitation energies and oscillator strengths:

Excited State 1: ?Spin -A 2.4398 eV 508.17 nm f=0.0004 50B -> 54B -0.13034 51B -> 54B -0.16026 52B -> 54B -0.41728 53B -> 54B 0.89641 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: ?Spin -A 2.8152 eV 440.41 nm f=0.0000 55A -> 56A 0.10134 52B -> 54B 0.89561 52B -> 55B 0.11560 53B -> 54B 0.41200

Excited State 3: ?Spin -A 2.8746 eV 431.30 nm f=0.0059 55A -> 56A 0.61045 55A -> 62A 0.12324 50B -> 55B 0.13093 51B -> 55B 0.11362 52B -> 54B -0.14395 52B -> 55B 0.63116 53B -> 55B -0.50344

Excited State 4: ?Spin -A 3.1813 eV 389.72 nm f=0.0273 55A -> 56A -0.14492 52B -> 55B 0.69000 53B -> 55B 0.68166 53B -> 56B 0.10561

237

Excited State 5: ?Spin -A 3.4185 eV 362.69 nm f=0.0347 53A -> 56A -0.39174 54A -> 56A -0.10713 54A -> 57A 0.26261 55A -> 56A 0.54697 55A -> 57A 0.28940 51B -> 56B -0.14081 52B -> 55B -0.18502 52B -> 56B 0.15976 52B -> 57B 0.20151 53B -> 55B 0.39967 53B -> 56B -0.43657 53B -> 57B 0.13116

Excited State 6: ?Spin -A 3.7773 eV 328.24 nm f=0.0322 53A -> 56A 0.26086 53A -> 57A 0.18539 54A -> 56A 0.18296 54A -> 57A -0.24017 55A -> 56A 0.46527 55A -> 57A -0.48273 51B -> 55B 0.19166 51B -> 56B 0.11116 52B -> 55B -0.24275 52B -> 56B -0.10885 52B -> 57B -0.31221 53B -> 55B 0.27872 53B -> 56B 0.23084 53B -> 57B -0.23902

Excited State 7: ?Spin -A 4.0827 eV 303.68 nm f=0.0056 53A -> 56A 0.30844 54A -> 56A 0.32932 54A -> 57A -0.11243 55A -> 56A 0.17061 55A -> 57A 0.71307 52B -> 56B -0.41675 52B -> 57B -0.22734 53B -> 56B 0.17750 53B -> 57B 0.10743

Excited State 8: ?Spin -A 4.1512 eV 298.67 nm f=0.0006 55A -> 58A 0.30198 50B -> 54B 0.13412 51B -> 54B 0.92010 53B -> 54B 0.16555

Excited State 9: ?Spin -A 4.2248 eV 293.47 nm f=0.0000 55A -> 58A 0.91183 55A -> 59A -0.17290 55A -> 61A 0.11585 51B -> 54B -0.30339

********************************************************************** 238

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Spectrum: B3LYP predicted IR spectra of 224a triplet

3-Benozthienyl(CF 3)carbene 224b singlet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -1.446154 2.477747 -0.000583 2 6 0 -2.776851 2.032118 0.000437 3 6 0 -3.060247 0.668405 0.000858 4 6 0 -1.983061 -0.219462 0.000237 5 6 0 -0.633524 0.197198 -0.000616 6 6 0 -0.381231 1.579382 -0.001119 7 16 0 -2.121682 -1.989394 0.000393 8 6 0 -0.434589 -2.162045 -0.000783 9 6 0 0.299885 -0.958019 -0.000946 10 6 0 1.686734 -1.165171 -0.001452 11 6 0 2.598538 0.018533 0.000268 12 9 0 3.906648 -0.333259 0.001829 13 9 0 2.433467 0.811354 1.108257 14 9 0 2.435379 0.811022 -1.108117 15 1 0 -1.239411 3.543528 -0.000932 239

16 1 0 -3.590709 2.750482 0.000819 17 1 0 -4.084674 0.309103 0.001433 18 1 0 0.633735 1.951840 -0.001932 19 1 0 0.031545 -3.138831 -0.001211 ------

Zero-point correction= 0.121930 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.599155

TD B3LYP of 224b singlet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 1.2514 eV 990.73 nm f=0.0006 54 -> 55 0.60685 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 3.2461 eV 381.94 nm f=0.0711 51 -> 55 -0.15896 52 -> 55 -0.19637 53 -> 55 0.62292

Excited State 3: Singlet-A 3.3409 eV 371.11 nm f=0.0123 52 -> 55 0.64781 53 -> 55 0.17179

Excited State 4: Singlet-A 3.7593 eV 329.81 nm f=0.0015 54 -> 56 0.69133

Excited State 5: Singlet-A 4.3925 eV 282.26 nm f=0.0001 54 -> 57 0.70494

Excited State 6: Singlet-A 4.6415 eV 267.12 nm f=0.0110 51 -> 55 -0.35438 54 -> 58 0.59650

Excited State 7: Singlet-A 4.9936 eV 248.28 nm f=0.0127 52 -> 56 -0.39411 52 -> 57 -0.22724 53 -> 56 0.41234 53 -> 57 -0.34705

Excited State 8: Singlet-A 5.0208 eV 246.94 nm f=0.2328 51 -> 55 0.49588 52 -> 57 -0.17465 54 -> 58 0.34696

Excited State 9: Singlet-A 5.3613 eV 231.26 nm f=0.1480 240

52 -> 56 0.32906 52 -> 57 -0.13303 53 -> 56 0.41461 53 -> 57 0.24656 54 -> 59 -0.26818

**********************************************************************

500 450 400 350 300 250 200 150 100 50 0 1850 1650 1450 1250 1050 850 650 450

Spectrum: B3LYP predicted IR spectra of 224b singlet

3-Benozthienyl(CF 3)carbene 224b triplet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -1.493063 2.485229 -0.000075 2 6 0 -2.827986 2.048353 0.000079 3 6 0 -3.129239 0.688317 0.000138 4 6 0 -2.071266 -0.225289 0.000030 5 6 0 -0.723034 0.195898 -0.000125 6 6 0 -0.442651 1.571603 -0.000171 7 16 0 -2.215637 -1.984314 0.000040 8 6 0 -0.495777 -2.161404 -0.000115 9 6 0 0.209850 -0.948015 -0.000213 241

10 6 0 1.589785 -0.907142 -0.000458 11 6 0 2.711544 0.026602 0.000015 12 9 0 3.894591 -0.633731 -0.000117 13 9 0 2.720539 0.852877 1.091272 14 9 0 2.720780 0.853722 -1.090610 15 1 0 -1.275678 3.548751 -0.000124 16 1 0 -3.634605 2.775091 0.000152 17 1 0 -4.159672 0.346818 0.000252 18 1 0 0.581633 1.925799 -0.000299 19 1 0 -0.053638 -3.148163 -0.000153 ------

Zero-point correction= 0.121163 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.599880 S2=2.033282\S2-1=0.\S2A=2.000298

TD B3LYP of 224b triplet

Excitation energies and oscillator strengths:

Excited State 1: ?Spin -A 2.5736 eV 481.75 nm f=0.0004 50B -> 54B 0.13318 51B -> 54B 0.17551 52B -> 54B -0.61546 53B -> 54B 0.76973 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: ?Spin -A 2.8831 eV 430.03 nm f=0.0062 55A -> 56A -0.65899 55A -> 62A 0.13616 50B -> 55B -0.13588 51B -> 55B -0.12220 52B -> 55B 0.71620 53B -> 55B -0.32409

Excited State 3: ?Spin -A 2.9347 eV 422.48 nm f=0.0000 52B -> 54B 0.78282 53B -> 54B 0.62060

Excited State 4: ?Spin -A 3.1823 eV 389.60 nm f=0.0239 55A -> 56A 0.14017 52B -> 55B 0.51515 53B -> 55B 0.82154

Excited State 5: ?Spin -A 3.4159 eV 362.97 nm f=0.0410 53A -> 56A -0.38652 54A -> 57A -0.26513 55A -> 56A 0.52339 55A -> 57A -0.28914 242

51B -> 56B 0.13173 52B -> 55B 0.31047 52B -> 56B 0.25762 52B -> 57B 0.14900 53B -> 55B -0.37715 53B -> 56B -0.36796 53B -> 57B 0.18399

Excited State 6: ?Spin -A 3.7712 eV 328.76 nm f=0.0366 53A -> 56A 0.25349 53A -> 57A -0.16807 54A -> 56A 0.15925 54A -> 57A 0.25446 55A -> 56A 0.43172 55A -> 57A 0.53028 51B -> 55B 0.19385 51B -> 56B -0.11005 52B -> 55B 0.31519 52B -> 56B -0.15251 52B -> 57B -0.22567 53B -> 55B -0.20213 53B -> 56B 0.17642 53B -> 57B -0.32803

Excited State 7: ?Spin -A 4.0847 eV 303.53 nm f=0.0058 53A -> 56A -0.33561 54A -> 56A -0.32851 54A -> 57A -0.14567 55A -> 56A -0.17437 55A -> 57A 0.68702 52B -> 56B 0.45865 52B -> 57B 0.26830

Excited State 8: ?Spin -A 4.1551 eV 298.39 nm f=0.0001 55A -> 58A 0.95271 55A -> 59A -0.15274 55A -> 61A 0.11826 51B -> 54B -0.15295

Excited State 9: ?Spin -A 4.2728 eV 290.17 nm f=0.0003 55A -> 58A 0.15251 50B -> 54B 0.15240 51B -> 54B 0.95488 53B -> 54B -0.16561

**********************************************************************

243

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Spectrum: B3LYP predicted IR spectra of 224b triplet

Bicyclic intermediate 232

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -3.194172 -1.691639 -0.011285 2 6 0 -3.688891 -0.536242 0.607820 3 6 0 -2.932941 0.638023 0.660969 4 6 0 -1.677255 0.670491 0.048370 5 6 0 -1.166329 -0.515588 -0.556222 6 6 0 -1.921519 -1.689291 -0.584062 7 16 0 -0.576132 2.079085 0.048111 8 6 0 0.616357 1.192145 -1.052540 9 6 0 0.195556 -0.239204 -0.947336 10 6 0 1.431455 0.028059 -0.591098 11 6 0 2.583984 -0.421356 0.220161 12 9 0 2.495118 -1.739093 0.516319 13 9 0 2.655609 0.266417 1.385000 14 9 0 3.766790 -0.236249 -0.419590 15 1 0 -3.795758 -2.594504 -0.035413 16 1 0 -4.679402 -0.547706 1.053010 17 1 0 -3.329783 1.522968 1.148249 18 1 0 -1.515758 -2.583135 -1.046510 19 1 0 0.803696 1.704946 -1.993328 ------244

Zero-point correction= 0.122834 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.605005

TD B3LYP of bicyclic intermediate 232

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 3.4494 eV 359.44 nm f=0.0416 54 -> 55 0.67707 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 4.4610 eV 277.93 nm f=0.0550 52 -> 55 0.18503 53 -> 55 0.58810 54 -> 56 -0.27402

Excited State 3: Singlet-A 4.7757 eV 259.61 nm f=0.0038 50 -> 55 0.10312 51 -> 55 0.10799 52 -> 55 0.47712 53 -> 56 -0.20936 54 -> 56 0.10809 54 -> 57 -0.39671

Excited State 4: Singlet-A 4.8195 eV 257.26 nm f=0.0095 52 -> 55 0.40405 53 -> 55 -0.15247 54 -> 57 0.51096 54 -> 58 -0.12066

Excited State 5: Singlet-A 4.9583 eV 250.05 nm f=0.0085 54 -> 56 -0.17248 54 -> 58 0.63707

Excited State 6: Singlet-A 5.0289 eV 246.54 nm f=0.2624 53 -> 55 0.21065 53 -> 57 -0.18587 54 -> 56 0.54574 54 -> 57 0.10562 54 -> 58 0.17211

Excited State 7: Singlet-A 5.4108 eV 229.14 nm f=0.0129 51 -> 55 0.59358 53 -> 56 -0.26791 54 -> 57 0.12593 54 -> 59 0.13292 245

Excited State 8: Singlet-A 5.6599 eV 219.06 nm f=0.0197 51 -> 55 -0.16980 54 -> 58 -0.11102 54 -> 59 0.65170

Excited State 9: Singlet-A 5.7745 eV 214.71 nm f=0.1023 50 -> 55 0.14111 51 -> 55 0.20344 51 -> 57 -0.13198 52 -> 57 -0.18410 53 -> 56 0.45808 53 -> 57 0.26422 54 -> 59 0.15024

**********************************************************************

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Spectrum: B3LYP predicted IR spectra of bicyclic intermediate 232

3-Benozthienyl(CF 3)ring-opened carbene 233 singlet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z 246

------1 6 0 3.427688 -1.589766 0.000111 2 6 0 3.938195 -0.276641 0.000655 3 6 0 3.082352 0.814672 0.000569 4 6 0 1.691430 0.600738 0.000004 5 6 0 1.130385 -0.714688 -0.000525 6 6 0 2.060612 -1.795011 -0.000504 7 16 0 0.674108 2.021648 -0.000348 8 6 0 -0.900684 1.370212 -0.000296 9 6 0 -1.188997 0.024367 -0.000286 10 6 0 -0.267575 -1.061133 -0.000927 11 6 0 -2.662161 -0.361936 0.000194 12 9 0 -2.991931 -1.089859 -1.088400 13 9 0 -3.485595 0.730953 0.000113 14 9 0 -2.991226 -1.089167 1.089478 15 1 0 4.109927 -2.434184 0.000175 16 1 0 5.011788 -0.111744 0.001132 17 1 0 3.483230 1.824881 0.000957 18 1 0 1.633449 -2.792399 -0.000954 19 1 0 -1.672835 2.134867 -0.000421 ------

Zero-point correction= 0.122261 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.611365

TD B3LYP of 3-benozthienyl(CF 3)ring-opened carbene 233 singlet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 1.2306 eV 1007.49 nm f=0.0011 54 -> 55 0.62559 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.6871 eV 461.40 nm f=0.0001 54 -> 56 0.69764

Excited State 3: Singlet-A 3.4790 eV 356.38 nm f=0.0008 54 -> 57 0.69883

Excited State 4: Singlet-A 3.6305 eV 341.51 nm f=0.0520 51 -> 55 -0.10580 52 -> 56 0.12612 53 -> 55 0.64979

Excited State 5: Singlet-A 4.2608 eV 290.99 nm f=0.0084 52 -> 55 0.24988 53 -> 56 -0.10210 54 -> 58 0.63455 54 -> 59 0.10597

247

Excited State 6: Singlet-A 4.3834 eV 282.85 nm f=0.0383 52 -> 55 0.53955 53 -> 56 -0.32455 54 -> 58 -0.25471

Excited State 7: Singlet-A 4.6149 eV 268.66 nm f=0.0032 54 -> 58 -0.12206 54 -> 59 0.68237 54 -> 61 -0.10264

Excited State 8: Singlet-A 5.0795 eV 244.09 nm f=0.0188 51 -> 55 0.35351 54 -> 60 0.57644

Excited State 9: Singlet-A 5.1651 eV 240.04 nm f=0.0719 51 -> 55 0.42714 52 -> 56 0.15756 53 -> 56 -0.23567 53 -> 57 -0.17290 54 -> 60 -0.35465 54 -> 61 0.14754 54 -> 62 0.10690

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Spectrum: B3LYP predicted IR spectra of ring-opened carbene 233 singlet

3-Benozthienyl(CF 3)ring-opened carbene 233 triplet 248

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.439967 -1.611420 0.000338 2 6 0 3.959827 -0.311280 0.007679 3 6 0 3.095258 0.786947 0.007616 4 6 0 1.713145 0.595514 0.000502 5 6 0 1.164696 -0.724137 -0.006023 6 6 0 2.065263 -1.816278 -0.006130 7 16 0 0.683019 2.057632 -0.003005 8 6 0 -0.943256 1.419781 -0.007447 9 6 0 -1.241392 0.071770 -0.011078 10 6 0 -0.238442 -0.886991 -0.011170 11 6 0 -2.685765 -0.376262 0.000967 12 9 0 -2.959278 -1.212686 -1.029103 13 9 0 -3.548262 0.664344 -0.089780 14 9 0 -2.991309 -1.046081 1.140070 15 1 0 4.110666 -2.465106 -0.000139 16 1 0 5.032959 -0.149181 0.013166 17 1 0 3.499607 1.795523 0.012960 18 1 0 1.655392 -2.821106 -0.011478 19 1 0 -1.713098 2.181697 -0.008629 ------

Zero-point correction= 0.121290 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.601476

TD B3LYP of 3-benozthienyl(CF 3)ring-opened carbene 233 triplet

Excitation energies and oscillator strengths:

Excited State 1: ?Spin -A 2.0429 eV 606.90 nm f=0.0073 55A -> 56A 1.00277 52B -> 55B -0.18321 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: ?Spin -A 2.8229 eV 439.20 nm f=0.0002 51B -> 54B 0.15209 53B -> 54B 0.98841

Excited State 3: ?Spin -A 2.8699 eV 432.01 nm f=0.0184 249

55A -> 57A 0.94165 52B -> 55B 0.11343 53B -> 55B 0.33627 53B -> 56B -0.12227

Excited State 4: ?Spin -A 3.3900 eV 365.74 nm f=0.0325 51A -> 57A 0.11424 54A -> 56A 0.11364 54A -> 57A -0.24673 55A -> 57A -0.27038 55A -> 62A -0.14775 52B -> 56B -0.17361 53B -> 55B 0.88733 53B -> 57B 0.16621

Excited State 5: ?Spin -A 3.5219 eV 352.04 nm f=0.0001 55A -> 58A 0.29448 55A -> 59A -0.10446 51B -> 54B -0.10511 52B -> 54B 0.93762

Excited State 6: ?Spin -A 3.5358 eV 350.66 nm f=0.0002 55A -> 58A 0.86608 55A -> 59A -0.28040 55A -> 60A -0.12120 55A -> 61A -0.17599 52B -> 54B -0.31970

Excited State 7: ?Spin -A 3.8614 eV 321.09 nm f=0.0027 51A -> 57A 0.11132 52A -> 56A -0.34286 54A -> 57A -0.40338 55A -> 62A 0.45730 51B -> 55B -0.25367 51B -> 57B -0.13345 52B -> 55B 0.45706 52B -> 56B -0.39186 53B -> 55B -0.15590 53B -> 56B 0.19922 53B -> 57B 0.38458

Excited State 8: ?Spin -A 4.0557 eV 305.70 nm f=0.0016 55A -> 58A 0.27918 55A -> 59A 0.94478 55A -> 61A -0.10613

Excited State 9: ?Spin -A 4.1718 eV 297.20 nm f=0.0038 54A -> 56A -0.47367 55A -> 62A -0.30859 51B -> 55B 0.21408 52B -> 55B 0.31732 52B -> 56B 0.21250 53B -> 56B 0.72137

250

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Spectrum: B3LYP predicted IR spectra of 3-Benozthienyl(CF 3)ring-opened carbene 233 triplet

3-Benozthienyl(CF 3)methylene cyclopropene 235

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -2.112260 -2.398297 -0.000326 2 6 0 -3.361154 -1.696528 -0.000458 3 6 0 -3.420162 -0.327147 -0.000225 4 6 0 -2.239392 0.496931 0.000231 5 6 0 -0.970224 -0.242114 -0.000398 6 6 0 -0.950015 -1.685395 -0.000145 7 6 0 0.933869 1.663749 -0.006149 8 6 0 0.218926 0.440229 -0.002262 9 6 0 1.632470 0.529624 -0.004171 10 16 0 -2.363503 2.183518 0.001903 11 6 0 2.965679 -0.140720 0.000092 12 9 0 3.966362 0.757676 -0.043254 13 9 0 3.085113 -0.958446 -1.066279 14 9 0 3.113125 -0.883952 1.116547 15 1 0 -2.098887 -3.483235 -0.000634 16 1 0 -4.285700 -2.268175 -0.000730 17 1 0 -4.376745 0.184270 -0.000151 251

18 1 0 0.012266 -2.190328 -0.000612 19 1 0 0.897274 2.741676 -0.008578 ------

Zero-point correction= 0.121340 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.584641

TD B3LYP 3-benozthienyl(CF 3)methylene cyclopropene 235

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 1.7386 eV 713.13 nm f=0.0001 53 -> 55 0.66537 53 -> 56 0.16729 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.0913 eV 592.85 nm f=0.0273 54 -> 55 0.58656 54 -> 56 -0.33835

Excited State 3: Singlet-A 2.2552 eV 549.76 nm f=0.0002 53 -> 55 -0.18832 53 -> 56 0.67648

Excited State 4: Singlet-A 2.7787 eV 446.19 nm f=0.1044 54 -> 55 0.23884 54 -> 56 0.55977

Excited State 5: Singlet-A 4.0588 eV 305.47 nm f=0.0001 53 -> 57 0.69892

Excited State 6: Singlet-A 4.2935 eV 288.77 nm f=0.0497 51 -> 55 0.25734 52 -> 55 0.58587 52 -> 56 -0.10941 54 -> 57 0.17920 54 -> 60 0.12512

Excited State 7: Singlet-A 4.3250 eV 286.67 nm f=0.0533 51 -> 55 0.27311 51 -> 56 0.11653 52 -> 55 -0.26210 54 -> 57 0.55673

Excited State 8: Singlet-A 4.6633 eV 265.87 nm f=0.0063 51 -> 55 0.40443 51 -> 56 -0.12898 52 -> 56 0.48035 252

54 -> 57 -0.20051

Excited State 9: Singlet-A 4.7014 eV 263.72 nm f=0.0097 54 -> 58 0.69183

**********************************************************************

600

500

400

300

200

100

0 1850 1650 1450 1250 1050 850 650 450

Spectrum: B3LYP predicted IR spectra of 3-benozthienyl(CF 3)methylene cyclopropene 235

3-Benozthienyl(CF 3)methylene cyclopropene 235 isomer

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.610698 1.269669 -0.000311 2 6 0 3.953086 -0.122357 -0.001215 3 6 0 2.993219 -1.099212 -0.001044 4 6 0 1.582521 -0.800843 0.000242 5 6 0 1.252375 0.630189 0.000507 6 6 0 2.296378 1.629691 0.000506 7 6 0 -0.048633 1.063562 0.000655 8 16 0 0.437199 -2.037054 0.001216 9 6 0 -0.996925 2.118642 0.000928 253

10 6 0 -1.454860 0.868643 0.000000 11 6 0 -2.686672 0.019104 -0.000516 12 9 0 -3.781538 0.821382 -0.002559 13 9 0 -2.746998 -0.753412 1.093981 14 9 0 -2.744758 -0.755949 -1.093257 15 1 0 4.393006 2.021622 -0.000380 16 1 0 5.002281 -0.406397 -0.002012 17 1 0 3.272231 -2.147449 -0.001676 18 1 0 2.008839 2.677945 0.001048 19 1 0 -1.219027 3.176436 0.001580 ------

TD B3LYP 3-benozthienyl(CF 3)methylene cyclopropene 235 isomer

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 1.7686 eV 701.05 nm f=0.0000 54 -> 55 0.67945 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.1886 eV 566.49 nm f=0.0001 54 -> 56 0.70505

Excited State 3: Singlet-A 2.2251 eV 557.21 nm f=0.0060 53 -> 56 0.68702

Excited State 4: Singlet-A 2.6343 eV 470.66 nm f=0.1105 53 -> 55 0.58264

Excited State 5: Singlet-A 4.0185 eV 308.54 nm f=0.0003 54 -> 57 0.69891

Excited State 6: Singlet-A 4.3153 eV 287.31 nm f=0.0387 51 -> 55 -0.32542 53 -> 57 0.60653

Excited State 7: Singlet-A 4.4822 eV 276.62 nm f=0.0040 53 -> 58 0.69737

Excited State 8: Singlet-A 4.5073 eV 275.07 nm f=0.0776 51 -> 55 -0.14950 52 -> 55 0.61075 53 -> 61 -0.20471

Excited State 9: Singlet-A 4.5318 eV 273.58 nm f=0.0016 52 -> 56 0.68410

********************************************************************** 254

450 400 350 300 250 200 150 100 50 0 1850 1650 1450 1250 1050 850 650 450

Spectrum: B3LYP predicted IR spectra of 3-benozthienyl(CF 3)methylene cyclopropene 235 isomer

3-Benozthienyl(CF 3)spiro product 234

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.003485 -1.800954 0.080012 2 6 0 3.771972 -0.758464 -0.456288 3 6 0 3.263058 0.544806 -0.596143 4 6 0 1.956185 0.737320 -0.172881 5 6 0 1.182397 -0.298461 0.365491 6 6 0 1.680507 -1.585592 0.504425 7 16 0 0.738052 2.041469 -0.061648 8 6 0 -0.077261 0.469276 0.636482 9 6 0 -1.053287 0.398651 1.749957 10 6 0 -1.503291 0.091761 0.563703 11 6 0 -2.637334 -0.341084 -0.288166 12 9 0 -3.760807 -0.528087 0.441454 13 9 0 -2.357870 -1.507301 -0.915833 14 9 0 -2.913158 0.576987 -1.240568 15 1 0 3.438477 -2.791949 0.166349 16 1 0 4.790403 -0.962892 -0.774546 255

17 1 0 3.868318 1.342393 -1.014292 18 1 0 1.085986 -2.396447 0.915522 19 1 0 -1.224079 0.527451 2.808317 ------

Zero-point correction= 0.121599 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.593918

TD B3LYP 3-benozthienyl(CF 3)spiro product 234

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 3.6895 eV 336.04 nm f=0.0174 54 -> 55 0.69725 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 4.0879 eV 303.30 nm f=0.0001 54 -> 56 0.16751 54 -> 57 0.66504

Excited State 3: Singlet-A 4.4424 eV 279.09 nm f=0.0083 53 -> 58 0.20076 54 -> 56 0.64153 54 -> 57 -0.15952

Excited State 4: Singlet-A 4.6611 eV 266.00 nm f=0.0036 53 -> 55 0.67731 54 -> 58 0.13913

Excited State 5: Singlet-A 5.0344 eV 246.27 nm f=0.1402 53 -> 55 -0.11980 53 -> 56 -0.19225 54 -> 58 0.61560

Excited State 6: Singlet-A 5.4059 eV 229.35 nm f=0.0121 54 -> 59 0.67362 54 -> 60 0.12653 54 -> 61 0.10220

Excited State 7: Singlet-A 5.4322 eV 228.24 nm f=0.0017 53 -> 56 0.15472 53 -> 57 0.67514

Excited State 8: Singlet-A 5.5641 eV 222.83 nm f=0.0024 51 -> 55 0.66584 53 -> 58 0.13072

Excited State 9: Singlet-A 5.6420 eV 219.75 nm f=0.0414 256

50 -> 55 0.10619 52 -> 55 0.64140

**********************************************************************

450 400 350 300 250 200 150 100 50 0 1850 1650 1450 1250 1050 850 650 450

Spectrum: B3LYP predicted IR spectra of 3-benozthienyl(CF 3)spiro product 234

Carbonyl Oxide

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -2.942165 2.098538 0.108531 2 6 0 -3.981099 1.153613 0.088691 3 6 0 -3.692657 -0.205847 0.026951 4 6 0 -2.350771 -0.594556 -0.016904 5 6 0 -1.284441 0.337289 -0.002134 6 6 0 -1.607274 1.708194 0.063508 7 16 0 -1.765793 -2.250867 -0.086862 257

8 6 0 -0.132299 -1.718905 -0.088346 9 6 0 0.017985 -0.342580 -0.042874 10 6 0 1.287878 0.337500 -0.060231 11 6 0 2.674331 -0.305233 0.081661 12 9 0 3.417009 -0.108561 -1.018520 13 9 0 2.587253 -1.649904 0.259792 14 9 0 3.321229 0.178272 1.151954 15 8 0 1.253701 1.615850 -0.197622 16 8 0 2.402249 2.351135 -0.219516 17 1 0 -3.181132 3.156247 0.158609 18 1 0 -5.014934 1.482992 0.122506 19 1 0 -4.486932 -0.945554 0.014490 20 1 0 -0.827676 2.457154 0.075172 21 1 0 0.649404 -2.459185 -0.136023 ------

Zero-point correction= 0.131265 (Hartree/Particle) Sum of electronic and zero-point Energies= -1231.997727

TD B3LYP of carbonyl oxide

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 2.2057 eV 562.11 nm f=0.0000 61 -> 63 0.67564 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 3.2042 eV 386.94 nm f=0.2495 59 -> 63 -0.21378 60 -> 63 -0.29829 62 -> 63 0.50660

Excited State 3: Singlet-A 3.4807 eV 356.20 nm f=0.0138 59 -> 63 -0.39349 60 -> 63 0.54061 62 -> 63 0.10185 62 -> 64 -0.11272

Excited State 4: Singlet-A 3.8328 eV 323.48 nm f=0.1319 58 -> 63 -0.10298 59 -> 63 0.48991 60 -> 63 0.28109 62 -> 63 0.22620

Excited State 5: Singlet-A 4.3711 eV 283.65 nm f=0.0385 58 -> 63 0.11334 62 -> 64 0.66158

Excited State 6: Singlet-A 4.7425 eV 261.43 nm f=0.0000 61 -> 64 0.69766 258

Excited State 7: Singlet-A 4.7531 eV 260.85 nm f=0.0118 60 -> 64 -0.28368 62 -> 65 0.62369

Excited State 8: Singlet-A 4.9474 eV 250.61 nm f=0.0001 62 -> 66 0.68598

Excited State 9: Singlet-A 5.0950 eV 243.35 nm f=0.0287 58 -> 63 0.54268 59 -> 64 0.15990 59 -> 65 0.21298 60 -> 64 0.24584 60 -> 65 -0.16337

**********************************************************************

3-benozthienyl(CF 3)benzylic chloride 231

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -2.973192 -1.989934 -0.581030 2 6 0 -3.974590 -1.017275 -0.400151 3 6 0 -3.640209 0.293573 -0.075441 4 6 0 -2.286028 0.619278 0.063395 5 6 0 -1.262718 -0.342344 -0.121200 6 6 0 -1.629672 -1.663509 -0.443227 7 16 0 -1.613761 2.190249 0.468615 8 6 0 0.003044 1.557277 0.389153 9 6 0 0.057547 0.231261 0.065777 10 6 0 1.300612 -0.590866 -0.066948 11 6 0 2.536937 0.158139 -0.576385 12 9 0 3.572454 -0.683135 -0.774237 13 9 0 2.958941 1.131579 0.260040 14 9 0 2.260787 0.737697 -1.769603 15 17 0 1.734257 -1.434249 1.503896 16 1 0 -3.254720 -3.009052 -0.827555 17 1 0 -5.019013 -1.292022 -0.511509 18 1 0 -4.411079 1.044508 0.067510 19 1 0 -0.872320 -2.431170 -0.572205 259

20 1 0 0.833570 2.219114 0.589569 21 1 0 1.141358 -1.401996 -0.779334 ------

Zero-point correction= 0.137819 (Hartree/Particle) Sum of electronic and zero-point Energies= -1542.501692

TD B3LYP 3-benozthienyl(CF 3)benzylic chloride 231

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 4.4334 eV 279.66 nm f=0.1026 62 -> 64 -0.20391 62 -> 65 0.10397 62 -> 66 -0.14393 63 -> 64 0.61203 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 4.7335 eV 261.93 nm f=0.0199 62 -> 64 0.51284 63 -> 64 0.18931 63 -> 66 0.41125

Excited State 3: Singlet-A 4.9869 eV 248.62 nm f=0.0079 61 -> 64 0.11707 62 -> 66 0.12580 63 -> 65 0.65021

Excited State 4: Singlet-A 5.1875 eV 239.01 nm f=0.0905 62 -> 64 0.29631 62 -> 65 0.39936 63 -> 66 -0.34617 63 -> 67 0.30254

Excited State 5: Singlet-A 5.2245 eV 237.31 nm f=0.0294 62 -> 64 -0.14107 62 -> 65 -0.21047 63 -> 66 0.17240 63 -> 67 0.60972

Excited State 6: Singlet-A 5.6842 eV 218.12 nm f=0.3387 61 -> 66 -0.17849 62 -> 64 -0.14525 62 -> 65 0.40998 62 -> 66 0.19946 62 -> 67 -0.21224 63 -> 66 0.31352 63 -> 71 -0.10215

260

Excited State 7: Singlet-A 5.7342 eV 216.22 nm f=0.0021 61 -> 64 -0.19141 62 -> 67 0.19894 63 -> 68 0.63179

Excited State 8: Singlet-A 5.7559 eV 215.40 nm f=0.0464 62 -> 65 0.14259 62 -> 67 0.62261 63 -> 66 0.11672 63 -> 68 -0.18222

Excited State 9: Singlet-A 5.8519 eV 211.87 nm f=0.0344 59 -> 64 -0.13033 61 -> 64 0.59182 61 -> 65 0.10230 63 -> 68 0.20972

**********************************************************************

3-Deutero-benozthienylCF 3diazirine (223i)

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -2.456826 -2.273690 -0.074086 2 6 0 -3.588643 -1.459936 -0.273274 3 6 0 -3.478073 -0.072847 -0.268967 4 6 0 -2.214266 0.490899 -0.059075 5 6 0 -1.064343 -0.311508 0.143523 6 6 0 -1.202505 -1.713377 0.132065 7 16 0 -1.813963 2.202283 -0.016614 8 6 0 -0.138622 1.835511 0.273921 9 6 0 0.123603 0.496706 0.337025 10 6 0 1.480234 -0.051821 0.585716 11 6 0 2.441220 -0.159857 -0.581177 12 9 0 1.918144 -0.908505 -1.579987 13 9 0 3.612465 -0.723162 -0.214855 14 9 0 2.721957 1.059340 -1.103824 15 7 0 2.103703 0.111944 1.925126 16 7 0 1.693230 -1.018230 1.694370 17 1 0 -2.566455 -3.353803 -0.084012 18 1 0 -4.559610 -1.918529 -0.434018 19 1 0 -4.349927 0.554839 -0.425376 20 1 0 -0.335035 -2.348214 0.280281 261

21 1 0 0.572125 2.643650 0.386433 ------Zero-point correction= 0.129416 (Hartree/Particle) Sum of electronic and zero-point Energies= -1191.132707

250

200

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100

0 1850 1650 1450 1250 1050 850 650 450

Spectrum: B3LYP predicted IR spectra of 3-BenozthienylCF 3diazirine (223i)

2-Deutero-3-benozthienyl(CF 3)carbene 224ia singlet

11 6 0 -2.805227 -0.386199 -0.003657 12 9 0 -3.575616 -1.110364 -0.850674 13 9 0 -3.088504 0.935219 -0.344208 14 9 0 -3.292286 -0.538140 1.257745 15 1 0 3.268600 -3.041264 -0.010992 16 1 0 4.888194 -1.165234 0.012893 17 1 0 4.091058 1.190514 0.020923 18 1 0 0.806418 -2.590543 -0.028598 19 1 0 -1.238540 2.048393 -0.028137 ------

Zero-point correction= 0.118604 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.604953

600

500

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100

0 1850 1650 1450 1250 1050 850 650

Spectrum: B3LYP predicted IR spectra of 2-deutero-3- benozthienyl(CF 3)carbene 224ia singlet

2-Deutero-3-benozthienyl(CF 3)carbene 224ib singlet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -1.446154 2.477747 -0.000583 263

2 6 0 -2.776851 2.032118 0.000437 3 6 0 -3.060247 0.668405 0.000858 4 6 0 -1.983061 -0.219462 0.000237 5 6 0 -0.633524 0.197198 -0.000616 6 6 0 -0.381231 1.579382 -0.001119 7 16 0 -2.121682 -1.989394 0.000393 8 6 0 -0.434589 -2.162045 -0.000783 9 6 0 0.299885 -0.958019 -0.000946 10 6 0 1.686734 -1.165171 -0.001452 11 6 0 2.598538 0.018533 0.000268 12 9 0 3.906648 -0.333259 0.001829 13 9 0 2.433467 0.811354 1.108257 14 9 0 2.435379 0.811022 -1.108117 15 1 0 -1.239411 3.543528 -0.000932 16 1 0 -3.590709 2.750482 0.000819 17 1 0 -4.084674 0.309103 0.001433 18 1 0 0.633735 1.951840 -0.001932 19 1 0 0.031545 -3.138831 -0.001211 ------

Zero-point correction= 0.118692 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.602392

300

250

200

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100

0 1850 1650 1450 1250 1050 850 650 450

Spectrum: B3LYP predicted IR spectra of 2-deutero-3- benozthienyl(CF 3)carbene 224ib singlet

264

2-Deutero-3-benozthienyl(CF 3)carbene 224ia triplet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 2.764869 -2.137692 -0.003186 2 6 0 3.762328 -1.147413 0.019193 3 6 0 3.425249 0.204764 0.023161 4 6 0 2.070282 0.548800 0.003843 5 6 0 1.057985 -0.432597 -0.018821 6 6 0 1.417710 -1.788501 -0.022041 7 16 0 1.395536 2.180867 0.004238 8 6 0 -0.220674 1.558057 -0.028002 9 6 0 -0.288154 0.154352 -0.034721 10 6 0 -1.451255 -0.588753 -0.060813 11 6 0 -2.893261 -0.349719 0.002912 12 9 0 -3.594076 -1.372435 -0.543469 13 9 0 -3.257138 0.789238 -0.663073 14 9 0 -3.353192 -0.200700 1.279746 15 1 0 3.048930 -3.185465 -0.005821 16 1 0 4.808695 -1.436851 0.033685 17 1 0 4.195707 0.969218 0.040613 18 1 0 0.646838 -2.553075 -0.039636 19 1 0 -1.059557 2.239589 -0.044629 ------Zero-point correction= 0.118041 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.604774

2-Deutero-3-benozthienyl(CF 3)carbene 224ib triplet

4 6 0 -2.071266 -0.225289 0.000030 5 6 0 -0.723034 0.195898 -0.000125 6 6 0 -0.442651 1.571603 -0.000171 7 16 0 -2.215637 -1.984314 0.000040 8 6 0 -0.495777 -2.161404 -0.000115 9 6 0 0.209850 -0.948015 -0.000213 10 6 0 1.589785 -0.907142 -0.000458 11 6 0 2.711544 0.026602 0.000015 12 9 0 3.894591 -0.633731 -0.000117 13 9 0 2.720539 0.852877 1.091272 14 9 0 2.720780 0.853722 -1.090610 15 1 0 -1.275678 3.548751 -0.000124 16 1 0 -3.634605 2.775091 0.000152 17 1 0 -4.159672 0.346818 0.000252 18 1 0 0.581633 1.925799 -0.000299 19 1 0 -0.053638 -3.148163 -0.000153 ------Zero-point correction= 0.117995 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.603048

2-Deutero-3-benozthienyl(CF 3)methylene cyclopropene 235i

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -2.112258 -2.398298 -0.000332 2 6 0 -3.361152 -1.696529 -0.000452 3 6 0 -3.420161 -0.327148 -0.000216 4 6 0 -2.239391 0.496930 0.000233 5 6 0 -0.970224 -0.242114 -0.000407 6 6 0 -0.950014 -1.685395 -0.000156 7 6 0 0.933868 1.663751 -0.006183 8 6 0 0.218925 0.440230 -0.002280 9 6 0 1.632470 0.529626 -0.004198 10 16 0 -2.363502 2.183518 0.001910 11 6 0 2.965678 -0.140721 0.000093 12 9 0 3.966358 0.757660 -0.043662 13 9 0 3.084973 -0.958781 -1.066036 14 9 0 3.113267 -0.883602 1.116762 15 1 0 -2.098885 -3.483236 -0.000644 16 1 0 -4.285698 -2.268177 -0.000719 17 1 0 -4.376745 0.184269 -0.000134 18 1 0 0.012267 -2.190328 -0.000633 266

19 1 0 0.897273 2.741678 -0.008620 ------

Zero-point correction= 0.118317 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.587663

600

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0 1850 1650 1450 1250 1050 850 650 450

Spectrum: B3LYP predicted IR spectra of 2-deutero-3- benozthieny(CF 3)methylene cyclopropene 235i

2-Deutero-3-benozthienyl(CF 3)methylene cyclopropene 235i isomer

8 16 0 0.437199 -2.037054 0.001216 9 6 0 -0.996925 2.118642 0.000928 10 6 0 -1.454860 0.868643 0.000000 11 6 0 -2.686672 0.019104 -0.000516 12 9 0 -3.781538 0.821382 -0.002559 13 9 0 -2.746998 -0.753412 1.093981 14 9 0 -2.744758 -0.755949 -1.093257 15 1 0 4.393006 2.021622 -0.000380 16 1 0 5.002281 -0.406397 -0.002012 17 1 0 3.272231 -2.147449 -0.001676 18 1 0 2.008839 2.677945 0.001048 19 1 0 -1.219027 3.176436 0.001580 ------

Zero-point correction= 0.118327 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.584005

500 450 400 350 300 250 200 150 100 50 0 1850 1650 1450 1250 1050 850 650 450

Spectrum: B3LYP predicted IR spectra of deutero-2-Deutero-3- benozthienyl(CF 3)methylene cyclopropene 235i isomer

Deutero bicyclic intermediate 232i

268

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.194280 -1.691605 -0.011303 2 6 0 3.688987 -0.536180 0.607765 3 6 0 2.932996 0.638054 0.660949 4 6 0 1.677273 0.670485 0.048416 5 6 0 1.166332 -0.515652 -0.556090 6 6 0 1.921587 -1.689318 -0.583981 7 6 0 -0.616321 1.192048 -1.052535 8 6 0 -0.195546 -0.239312 -0.947192 9 6 0 -1.431459 0.028014 -0.591043 10 16 0 0.576173 2.079059 0.048052 11 6 0 -2.584066 -0.421322 0.220143 12 9 0 -2.655609 0.266311 1.385072 13 9 0 -2.495401 -1.739111 0.516138 14 9 0 -3.766838 -0.235955 -0.419595 15 1 0 3.795920 -2.594431 -0.035476 16 1 0 4.679525 -0.547603 1.052890 17 1 0 3.329835 1.523021 1.148191 18 1 0 1.515814 -2.583183 -1.046374 19 1 0 -0.803606 1.704774 -1.993374 ------

Zero-point correction= 0.119510 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.608329

350

300

250

200

150

100

0 1900 1700 1500 1300 1100 900 700 500

269

Spectrum: B3LYP predicted IR spectra of deutero bicyclic intermediate 232i

2-Deutero-3-Benozthienyl(CF 3)ring-opened carbene 233i singlet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.427688 -1.589766 0.000111 2 6 0 3.938195 -0.276641 0.000655 3 6 0 3.082352 0.814672 0.000569 4 6 0 1.691430 0.600738 0.000004 5 6 0 1.130385 -0.714688 -0.000525 6 6 0 2.060612 -1.795011 -0.000504 7 16 0 0.674108 2.021648 -0.000348 8 6 0 -0.900684 1.370212 -0.000296 9 6 0 -1.188997 0.024367 -0.000286 10 6 0 -0.267575 -1.061133 -0.000927 11 6 0 -2.662161 -0.361936 0.000194 12 9 0 -2.991931 -1.089859 -1.088400 13 9 0 -3.485595 0.730953 0.000112 14 9 0 -2.991226 -1.089166 1.089479 15 1 0 4.109927 -2.434184 0.000175 16 1 0 5.011788 -0.111744 0.001132 17 1 0 3.483230 1.824881 0.000957 18 1 0 1.633449 -2.792399 -0.000954 19 1 0 -1.672835 2.134867 -0.000421 ------

Zero-point correction= 0.119007 (Hartree/Particle) Sum of electronic and zero-point Energies= -1081.614619

270

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0 1850 1650 1450 1250 1050 850 650 450

Spectrum: B3LYP predicted IR spectra of 2-deutero-3-

Benozthienyl(CF 3)ring-opened carbene 233i singlet

2-Deutero-3-Benozthienyl(CF 3)spiro product 234i

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.003484 -1.800955 0.080012 2 6 0 3.771971 -0.758465 -0.456288 3 6 0 3.263058 0.544804 -0.596144 4 6 0 1.956185 0.737319 -0.172881 5 6 0 1.182396 -0.298460 0.365491 6 6 0 1.680505 -1.585591 0.504426 7 16 0 0.738052 2.041469 -0.061649 8 6 0 -0.077261 0.469278 0.636482 9 6 0 -1.053287 0.398654 1.749957 10 6 0 -1.503291 0.091763 0.563703 11 6 0 -2.637334 -0.341084 -0.288166 12 9 0 -3.760805 -0.528093 0.441455 13 9 0 -2.357866 -1.507299 -0.915836 14 9 0 -2.913162 0.576988 -1.240566 15 1 0 3.438475 -2.791950 0.166350 16 1 0 4.790402 -0.962894 -0.774546 17 1 0 3.868318 1.342392 -1.014292 18 1 0 1.085985 -2.396447 0.915523 19 1 0 -1.224079 0.527454 2.808316 ------271

Zero-point correction= 0.118607 (Hartree/Particle)

450 400 350 300 250 200 150 100 50 0 1850 1725 1600 1475 1350 1225 1100 975 850 725 600 475

Spectrum: B3LYP predicted IR spectra of 2-deutero-3-

Benozthienyl(CF 3)spiro product 234i

N-Methyl-2-indolyl(CF 3)diazirine (244)

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 4.298625 -0.846101 -0.236626 2 6 0 4.243481 0.565461 -0.283799 3 6 0 3.040827 1.249082 -0.142540 4 6 0 1.880899 0.483449 0.051223 5 6 0 1.914801 -0.939266 0.096843 6 6 0 3.148729 -1.601673 -0.048572 7 7 0 0.573693 0.891988 0.223897 8 6 0 -0.219874 -0.247190 0.364607 9 6 0 0.567000 -1.375266 0.296683 10 6 0 0.135569 2.277959 0.191201 272

11 6 0 -1.678627 -0.178847 0.569812 12 6 0 -2.591594 -0.154379 -0.641240 13 9 0 -3.884194 0.020375 -0.290630 14 9 0 -2.512052 -1.304631 -1.347365 15 9 0 -2.255710 0.853871 -1.484627 16 7 0 -2.257043 -0.805206 1.789273 17 7 0 -2.240177 0.416072 1.820309 18 1 0 5.257077 -1.343269 -0.351594 19 1 0 5.159746 1.128320 -0.435302 20 1 0 3.008576 2.333202 -0.184448 21 1 0 3.197362 -2.686361 -0.015593 22 1 0 0.210428 -2.391959 0.384378 23 1 0 0.753971 2.879137 0.864513 24 1 0 -0.899104 2.346284 0.523900 25 1 0 0.205218 2.688757 -0.822156 ------

Zero-point correction= 0.176103 (Hartree/Particle) Sum of electronic and zero-point Energies= -887.567841

TD B3LYP of diazirine 244

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 2.5082 eV 494.31 nm f=0.0055 61 -> 62 0.69402 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 3.0017 eV 413.05 nm f=0.0018 60 -> 62 0.69702 61 -> 62 -0.10099

Excited State 3: Singlet-A 4.0076 eV 309.38 nm f=0.0001 58 -> 62 0.67224

Excited State 4: Singlet-A 4.4554 eV 278.28 nm f=0.0072 59 -> 62 0.66638 61 -> 63 0.18429

Excited State 5: Singlet-A 4.4845 eV 276.47 nm f=0.0856 59 -> 62 -0.21957 60 -> 63 -0.17836 60 -> 65 -0.14155 61 -> 63 0.58324

Excited State 6: Singlet-A 4.7714 eV 259.85 nm f=0.1311 60 -> 63 0.54922 61 -> 63 0.17989 273

61 -> 65 0.36441

Excited State 7: Singlet-A 5.2558 eV 235.90 nm f=0.0106 61 -> 64 0.69896

Excited State 8: Singlet-A 5.6104 eV 220.99 nm f=0.0389 61 -> 65 -0.19316 61 -> 66 0.64069 61 -> 67 -0.10281 61 -> 68 0.10649

Excited State 9: Singlet-A 5.7053 eV 217.31 nm f=0.2564 59 -> 63 0.17835 60 -> 63 -0.18228 60 -> 65 0.11652 61 -> 65 0.38811 61 -> 66 0.25598 61 -> 68 -0.30553 61 -> 69 0.23637

**********************************************************************

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Spectrum: B3LYP predicted IR spectra of diazirine 244

274

N-Methyl-2-indolyl(CF 3)carbene (245a) singlet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 4.199872 -0.478284 -0.057145 2 6 0 3.882368 0.912373 -0.066663 3 6 0 2.581173 1.378438 -0.030865 4 6 0 1.542776 0.419242 0.017457 5 6 0 1.848425 -0.988637 0.023670 6 6 0 3.200610 -1.424003 -0.014611 7 7 0 0.197064 0.596367 0.062473 8 6 0 -0.436735 -0.698115 0.084597 9 6 0 0.624250 -1.652392 0.077833 10 6 0 -0.439221 1.909258 0.101027 11 6 0 -1.744585 -1.139323 0.064701 12 6 0 -2.903199 -0.216958 -0.035386 13 9 0 -4.073540 -0.871943 -0.242054 14 9 0 -2.831200 0.694844 -1.067435 15 9 0 -3.083811 0.495377 1.128384 16 1 0 5.241446 -0.781860 -0.087214 17 1 0 4.695836 1.631422 -0.108425 18 1 0 2.375245 2.442653 -0.051910 19 1 0 3.429197 -2.485657 -0.010158 20 1 0 0.434106 -2.716437 0.098442 21 1 0 -1.348342 1.864155 0.695237 22 1 0 -0.687277 2.258843 -0.905421 23 1 0 0.242902 2.618216 0.574380 ------

Zero-point correction= 0.165849 (Hartree/Particle) Sum of electronic and zero-point Energies= -778.045729

TD B3LYP of carbene 245a singlet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 1.2547 eV 988.16 nm f=0.0007 54 -> 55 0.61539 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

275

Excited State 2: Singlet-A 2.7630 eV 448.73 nm f=0.0331 52 -> 55 -0.10654 53 -> 55 0.64201

Excited State 3: Singlet-A 3.9727 eV 312.09 nm f=0.5118 52 -> 55 0.59181 53 -> 57 0.15470

Excited State 4: Singlet-A 4.2589 eV 291.12 nm f=0.0047 54 -> 56 0.68291

Excited State 5: Singlet-A 4.6100 eV 268.95 nm f=0.0077 51 -> 55 0.65508 52 -> 56 0.10355 53 -> 56 0.11906

Excited State 6: Singlet-A 4.8293 eV 256.73 nm f=0.0003 54 -> 56 0.11300 54 -> 57 0.69175

Excited State 7: Singlet-A 5.1647 eV 240.06 nm f=0.0016 54 -> 58 0.67765 54 -> 60 -0.15933

Excited State 8: Singlet-A 5.2172 eV 237.64 nm f=0.0682 51 -> 56 0.13587 52 -> 56 -0.11874 52 -> 57 -0.11816 53 -> 56 0.62064 53 -> 57 -0.15311

Excited State 9: Singlet-A 5.4875 eV 225.94 nm f=0.0106 54 -> 59 0.67157 54 -> 60 -0.15664

**********************************************************************

276

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Spectrum: B3LYP predicted IR spectra of carbene 245a singlet

N-Methyl-2-indolyl(CF 3)carbene (245a) triplet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -4.261593 -0.532273 0.066776 2 6 0 -3.997682 0.856165 0.080328 3 6 0 -2.695771 1.354717 0.035006 4 6 0 -1.648656 0.429613 -0.031091 5 6 0 -1.894227 -0.980555 -0.036682 6 6 0 -3.224979 -1.452233 0.009826 7 7 0 -0.284330 0.639812 -0.098130 8 6 0 0.364018 -0.607662 -0.110812 9 6 0 -0.635603 -1.618985 -0.086853 10 6 0 0.368420 1.938326 -0.082831 11 6 0 1.718306 -0.824572 -0.160033 12 6 0 3.019837 -0.201553 0.026754 13 9 0 3.999419 -1.132691 0.123816 14 9 0 3.090063 0.569225 1.158068 15 9 0 3.377416 0.632149 -1.003478 16 1 0 -5.289941 -0.877959 0.105176 277

17 1 0 -4.828269 1.553821 0.130923 18 1 0 -2.514259 2.424016 0.056197 19 1 0 -3.426338 -2.519367 0.003830 20 1 0 -0.427611 -2.679212 -0.101179 21 1 0 1.268283 1.909909 -0.699105 22 1 0 0.641224 2.244615 0.933401 23 1 0 -0.307280 2.681434 -0.510316 ------

Zero-point correction= 0.164475 (Hartree/Particle) Sum of electronic and zero-point Energies= -778.041620

TD B3LYP of carbene 245a triplet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 0.3477 eV 3565.41 nm f=0.0002 54 -> 55 0.47825 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.5914 eV 478.45 nm f=0.0359 52 -> 55 -0.12677 53 -> 55 0.63261

Excited State 3: Singlet-A 3.5773 eV 346.58 nm f=0.0018 52 -> 55 0.10757 54 -> 56 0.67473

Excited State 4: Singlet-A 3.8869 eV 318.98 nm f=0.5010 52 -> 55 0.58325 53 -> 57 0.16388 54 -> 56 -0.10587

Excited State 5: Singlet-A 4.1783 eV 296.73 nm f=0.0020 54 -> 56 -0.10868 54 -> 57 0.69198

Excited State 6: Singlet-A 4.4181 eV 280.63 nm f=0.0039 51 -> 55 0.65835 53 -> 56 -0.12118

Excited State 7: Singlet-A 4.4996 eV 275.54 nm f=0.0018 54 -> 58 0.67028 54 -> 59 -0.11362 54 -> 60 0.17738

Excited State 8: Singlet-A 4.8499 eV 255.64 nm f=0.0032 278

54 -> 59 0.68132 54 -> 60 0.10652

Excited State 9: Singlet-A 4.9385 eV 251.06 nm f=0.0233 54 -> 58 -0.19532 54 -> 60 0.59997 54 -> 61 -0.17701 54 -> 62 0.19782

**********************************************************************

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Spectrum: B3LYP predicted IR spectra of carbene 245a triplet

1 CF3

N CH N-Methyl-2-indolyl(CF 3)carbene (245b) singlet 3

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.821960 -1.327487 0.007859 2 6 0 4.077299 0.079440 0.009155 3 6 0 3.063488 1.015270 0.002489 4 6 0 1.732937 0.532269 -0.005514 5 6 0 1.455314 -0.884562 -0.007464 279

6 6 0 2.535264 -1.811653 -0.000366 7 7 0 0.569666 1.209524 -0.011398 8 6 0 -0.522591 0.277613 -0.018636 9 6 0 0.069880 -1.025895 -0.017082 10 6 0 0.424698 2.657522 -0.010065 11 6 0 -1.809934 0.757797 -0.017053 12 6 0 -2.950485 -0.189553 -0.000761 13 9 0 -3.848519 0.135079 -0.967508 14 9 0 -3.576193 -0.103337 1.205340 15 9 0 -2.730448 -1.549353 -0.188449 16 1 0 4.663374 -2.012812 0.013453 17 1 0 5.108935 0.419383 0.015727 18 1 0 3.278606 2.078171 0.003675 19 1 0 2.335361 -2.878793 -0.001512 20 1 0 -0.495442 -1.945292 -0.022422 21 1 0 -0.644847 2.870939 -0.010339 22 1 0 0.888441 3.088889 -0.902977 23 1 0 0.887358 3.086788 0.884364 ------

Zero-point correction= 0.165820 (Hartree/Particle) Sum of electronic and zero-point Energies= -778.055668

TD B3LYP of carbene 245b singlet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 1.4337 eV 864.78 nm f=0.0012 54 -> 55 0.62965 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.7611 eV 449.04 nm f=0.0349 53 -> 55 0.63955

Excited State 3: Singlet-A 3.9877 eV 310.92 nm f=0.5083 52 -> 55 0.59399 53 -> 57 0.18288

Excited State 4: Singlet-A 4.5007 eV 275.48 nm f=0.0011 54 -> 56 0.68698

Excited State 5: Singlet-A 4.5776 eV 270.85 nm f=0.0041 51 -> 55 0.65853 53 -> 56 0.13645

Excited State 6: Singlet-A 4.9710 eV 249.41 nm f=0.0002 54 -> 57 0.69630

280

Excited State 7: Singlet-A 5.2547 eV 235.95 nm f=0.0286 51 -> 56 0.13282 52 -> 57 -0.12204 53 -> 56 0.62145 53 -> 57 0.12914 54 -> 58 0.10621

Excited State 8: Singlet-A 5.3263 eV 232.78 nm f=0.0093 54 -> 58 0.65536 54 -> 59 -0.14709 54 -> 60 -0.14815

Excited State 9: Singlet-A 5.6337 eV 220.08 nm f=0.3624 50 -> 55 0.39368 52 -> 56 0.15371 53 -> 56 -0.10578 53 -> 57 0.44824 54 -> 58 0.14836 54 -> 59 0.16410

**********************************************************************

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Spectrum: B3LYP predicted IR spectra of carbene 245b singlet

281

N-Methyl-2-indolyl(CF 3)carbene (245b) triplet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -3.956160 -1.227764 0.028717 2 6 0 -4.152606 0.171687 0.041913 3 6 0 -3.077624 1.061064 0.020538 4 6 0 -1.790272 0.517212 -0.017490 5 6 0 -1.567761 -0.897028 -0.023635 6 6 0 -2.678594 -1.769084 -0.003240 7 7 0 -0.566262 1.151241 -0.053659 8 6 0 0.447916 0.183936 -0.061233 9 6 0 -0.168949 -1.100887 -0.053719 10 6 0 -0.358203 2.586304 0.001892 11 6 0 1.782546 0.501546 -0.086022 12 6 0 3.062566 -0.192475 0.008671 13 9 0 3.631197 -0.096382 1.246135 14 9 0 3.978924 0.305404 -0.863481 15 9 0 2.944099 -1.528241 -0.255697 16 1 0 -4.820118 -1.884894 0.046616 17 1 0 -5.164232 0.565210 0.071484 18 1 0 -3.243191 2.133375 0.035812 19 1 0 -2.529313 -2.844677 -0.010288 20 1 0 0.367808 -2.037374 -0.073505 21 1 0 0.674434 2.805455 -0.275120 22 1 0 -0.545330 2.980778 1.007843 23 1 0 -1.021368 3.089348 -0.708199 ------

Zero-point correction= 0.164397 (Hartree/Particle) Sum of electronic and zero-point Energies= -778.044779

TD B3LYP N-Methyl-2-indolyl(CF 3)carbene (245b) triplet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 0.5214 eV 2377.90 nm f=0.0004 54 -> 55 0.53849 This state for optimization and/or second-order correction. 282

Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.6148 eV 474.16 nm f=0.0354 52 -> 55 -0.11724 53 -> 55 0.63193

Excited State 3: Singlet-A 3.7310 eV 332.30 nm f=0.0052 54 -> 56 0.67607

Excited State 4: Singlet-A 3.9042 eV 317.57 nm f=0.4777 52 -> 55 0.58051 53 -> 57 -0.17062 54 -> 56 0.11332

Excited State 5: Singlet-A 4.2874 eV 289.18 nm f=0.0140 54 -> 57 0.68980

Excited State 6: Singlet-A 4.4093 eV 281.19 nm f=0.0031 51 -> 55 0.66057 53 -> 56 -0.12806

Excited State 7: Singlet-A 4.6465 eV 266.83 nm f=0.0070 54 -> 58 0.66738 54 -> 59 0.12704 54 -> 60 0.16423

Excited State 8: Singlet-A 4.9825 eV 248.84 nm f=0.0017 54 -> 58 -0.11223 54 -> 59 0.67884

Excited State 9: Singlet-A 5.0793 eV 244.10 nm f=0.0073 53 -> 56 -0.14031 54 -> 58 -0.18733 54 -> 60 0.60671 54 -> 61 -0.14749 54 -> 62 -0.15807

**********************************************************************

283

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Spectrum: B3LYP predicted IR spectra of carbene (245a) triplet

N-Methyl-2-indolyl(CF 3) quinoimine 246a

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -4.109280 -1.201033 0.002478 2 6 0 -4.283416 0.235126 0.007694 3 6 0 -3.217741 1.074256 0.006106 4 6 0 -1.840928 0.569259 -0.001726 5 6 0 -1.671146 -0.916439 -0.004074 6 6 0 -2.864520 -1.741813 -0.003139 7 6 0 -0.452156 -1.547308 -0.005479 8 6 0 0.832884 -0.975238 -0.004762 9 6 0 2.005031 -0.651214 -0.007453 10 7 0 -0.774119 1.299196 -0.007548 11 6 0 -0.868271 2.747506 -0.004604 12 6 0 3.360428 -0.132841 0.001055 13 9 0 4.004196 -0.427973 1.160742 14 9 0 3.395359 1.216478 -0.136912 15 9 0 4.107218 -0.651347 -1.008702 16 1 0 -4.986059 -1.841121 0.003478 17 1 0 -5.292334 0.639043 0.012695 18 1 0 -3.372697 2.146756 0.009473 284

19 1 0 -2.733782 -2.820551 -0.006488 20 1 0 -0.457041 -2.636452 -0.005809 21 1 0 -1.390762 3.129512 -0.893983 22 1 0 0.141117 3.164708 -0.001746 23 1 0 -1.395873 3.127755 0.882480 ------

Zero-point correction= 0.162989 (Hartree/Particle) Sum of electronic and zero-point Energies= -778.031489

TD B3LYP of N-methyl-2-indolyl(CF 3) quinoimine 246a

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 2.4988 eV 496.18 nm f=0.0000 53 -> 55 0.68055 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.7173 eV 456.28 nm f=0.1707 54 -> 55 0.58773

Excited State 3: Singlet-A 4.0695 eV 304.67 nm f=0.0007 51 -> 55 0.68985

Excited State 4: Singlet-A 4.0916 eV 303.02 nm f=0.0897 52 -> 55 0.61250 54 -> 56 0.29049

Excited State 5: Singlet-A 4.6407 eV 267.17 nm f=0.0068 50 -> 55 0.60531 54 -> 56 -0.19694 54 -> 59 0.27390

Excited State 6: Singlet-A 4.8550 eV 255.38 nm f=0.0003 54 -> 57 0.68714

Excited State 7: Singlet-A 4.9283 eV 251.58 nm f=0.1840 50 -> 55 0.12144 52 -> 55 -0.18437 53 -> 57 -0.14768 54 -> 56 0.54957 54 -> 59 0.21349

Excited State 8: Singlet-A 5.2005 eV 238.41 nm f=0.0000 53 -> 56 0.69802

Excited State 9: Singlet-A 5.3384 eV 232.25 nm f=0.0015 54 -> 58 0.69067 285

*******************************************************************

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Spectrum: B3LYP predicted IR spectra of 2-N-Methyl-indolyl(CF 3) quinoimine 246a

N-Methyl-2-indolyl(CF 3) quinoimine 246b

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -4.077557 -1.046353 0.160835 2 6 0 -4.079112 0.138481 0.995285 3 6 0 -3.018373 0.981252 0.995054 4 6 0 -1.873991 0.755641 0.101505 5 6 0 -1.738041 -0.640647 -0.426693 6 6 0 -2.967239 -1.410610 -0.531803 7 6 0 -0.551003 -1.277551 -0.687823 8 6 0 0.748773 -0.839738 -0.371998 9 6 0 1.893760 -0.543189 -0.093848 10 6 0 3.254438 -0.175484 0.263335 11 9 0 3.651913 -0.762828 1.419551 12 9 0 3.383962 1.164638 0.433010 13 9 0 4.142096 -0.544062 -0.694023 14 7 0 -1.200870 1.811847 -0.219120 15 6 0 -0.230368 1.868648 -1.285546 286

16 1 0 -4.967108 -1.668310 0.124341 17 1 0 -4.958769 0.362315 1.591383 18 1 0 -3.020787 1.917930 1.542374 19 1 0 -2.943358 -2.339898 -1.094959 20 1 0 -0.604707 -2.290641 -1.085850 21 1 0 0.782338 1.888931 -0.863129 22 1 0 -0.371050 2.820661 -1.808447 23 1 0 -0.279936 1.043646 -2.008535 ------

Zero-point correction= 0.163296 (Hartree/Particle) Sum of electronic and zero-point Energies= -778.024404

TD B3LYP N-Methyl-2-indolyl(CF 3)quinoimine 246b

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 2.8325 eV 437.72 nm f=0.0716 53 -> 55 -0.40240 54 -> 55 0.49340 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.9632 eV 418.41 nm f=0.0598 52 -> 55 -0.11378 53 -> 55 0.54744 54 -> 55 0.34774

Excited State 3: Singlet-A 4.2255 eV 293.42 nm f=0.1022 52 -> 55 0.57471 54 -> 56 0.34074

Excited State 4: Singlet-A 4.3653 eV 284.02 nm f=0.0037 50 -> 55 0.36943 51 -> 55 0.57767

Excited State 5: Singlet-A 4.6869 eV 264.53 nm f=0.0678 50 -> 55 0.22151 52 -> 55 -0.15685 54 -> 56 0.40404 54 -> 57 0.45926

Excited State 6: Singlet-A 4.7451 eV 261.29 nm f=0.0176 50 -> 55 0.44329 51 -> 55 -0.29698 54 -> 57 -0.31720 54 -> 58 -0.29828

Excited State 7: Singlet-A 5.0704 eV 244.52 nm f=0.1960 52 -> 55 -0.17885 287

54 -> 56 0.37681 54 -> 57 -0.37860 54 -> 58 0.29419

Excited State 8: Singlet-A 5.2930 eV 234.24 nm f=0.0588 53 -> 56 0.63216 54 -> 58 -0.19952

Excited State 9: Singlet-A 5.4679 eV 226.75 nm f=0.0204 53 -> 56 0.13221 54 -> 58 0.20151 54 -> 59 0.63079

**********************************************************************

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Spectrum: B3LYP predicted IR spectra of 2-N-Methyl-indolyl(CF 3) quinoimine 246b

N-Methyl-2-indolyl(CF 3)ring-opened carbene 236b

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.874815 -0.224688 0.416810 2 6 0 3.433006 1.110195 0.350537 288

3 6 0 2.109866 1.411553 0.064553 4 6 0 1.172914 0.373335 -0.136009 5 6 0 1.620699 -0.986623 -0.107421 6 6 0 2.976317 -1.252145 0.188349 7 7 0 -0.173721 0.652718 -0.370892 8 6 0 -1.060737 -0.406159 -0.270873 9 6 0 -0.644654 -1.680222 -0.527248 10 6 0 0.686507 -1.969377 -0.595480 11 6 0 -0.581940 2.018294 -0.736205 12 6 0 -2.451615 -0.115369 0.249550 13 9 0 -3.030829 -1.210942 0.755891 14 9 0 -3.285209 0.368326 -0.721561 15 9 0 -2.433437 0.831835 1.231313 16 1 0 4.916652 -0.442880 0.629405 17 1 0 4.132164 1.920933 0.532293 18 1 0 1.795708 2.447811 0.042684 19 1 0 3.305593 -2.287233 0.207178 20 1 0 1.068306 -2.866080 -1.081604 21 1 0 -1.611459 2.001618 -1.085385 22 1 0 0.055038 2.391532 -1.543182 23 1 0 -0.511744 2.689534 0.124683 ------Zero-point correction= 0.166896 (Hartree/Particle) Sum of electronic and zero-point Energies= -778.062761

TD B3LYP N-Methyl-2-indolyl(CF 3)ring-opened carbene 236b

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 2.6042 eV 476.10 nm f=0.0472 54 -> 55 0.60567 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 3.7958 eV 326.64 nm f=0.0563 52 -> 56 -0.10442 53 -> 55 0.61625 54 -> 56 0.16746

Excited State 3: Singlet-A 3.8717 eV 320.23 nm f=0.0060 52 -> 55 -0.11644 53 -> 55 -0.19776 54 -> 56 0.64866

Excited State 4: Singlet-A 4.2463 eV 291.98 nm f=0.0894 52 -> 55 0.62373 53 -> 56 0.20383 54 -> 56 0.13248

Excited State 5: Singlet-A 4.3832 eV 282.86 nm f=0.0142 289

53 -> 56 -0.10463 54 -> 57 0.68075

Excited State 6: Singlet-A 4.9388 eV 251.04 nm f=0.0077 54 -> 58 0.69345 54 -> 60 -0.10114

Excited State 7: Singlet-A 5.1205 eV 242.13 nm f=0.0110 51 -> 55 0.61654 53 -> 56 -0.20729 53 -> 57 0.14407 54 -> 65 0.10807

Excited State 8: Singlet-A 5.3419 eV 232.10 nm f=0.0134 53 -> 56 0.17399 54 -> 59 0.62727 54 -> 60 -0.22141

Excited State 9: Singlet-A 5.4627 eV 226.97 nm f=0.0641 53 -> 56 0.15148 54 -> 58 0.10866 54 -> 59 0.17932 54 -> 60 0.60852 54 -> 61 0.18318

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Spectrum: B3LYP predicted IR spectra of 2-N-Methyl-indolyl(CF 3)ring- opened carbene 236b

290

N-Methyl-2-indolyl(CF 3)ring-opened carbene 247

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -3.369962 -1.676228 0.000053 2 6 0 -3.822115 -0.341762 0.000150 3 6 0 -2.926709 0.716570 0.000100 4 6 0 -1.536543 0.466534 -0.000054 5 6 0 -1.073776 -0.876212 -0.000115 6 6 0 -2.013023 -1.934982 -0.000074 7 7 0 -0.580570 1.493254 -0.000123 8 6 0 0.762701 1.337929 -0.000203 9 6 0 1.184940 -0.037922 -0.000259 10 6 0 0.332135 -1.107246 -0.000204 11 6 0 -1.073832 2.885557 -0.000029 12 6 0 2.680123 -0.258536 -0.000053 13 9 0 3.274880 0.280292 1.090168 14 9 0 3.275969 0.283535 -1.087814 15 9 0 3.001371 -1.584929 -0.001814 16 1 0 -4.085058 -2.492605 0.000085 17 1 0 -4.888079 -0.134316 0.000266 18 1 0 -3.306075 1.730012 0.000194 19 1 0 -1.643419 -2.956641 -0.000134 20 1 0 0.695924 -2.131441 -0.000282 21 1 0 -0.192528 3.521404 -0.000292 22 1 0 -1.674931 3.079281 0.893775 23 1 0 -1.675444 3.079235 -0.893494 ------

Zero-point correction= 0.167633 (Hartree/Particle) Sum of electronic and zero-point Energies= -778.092935

TD B3LYP N-Methyl-2-indolyl(CF 3)ring-opened carbene 247

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 2.2196 eV 558.60 nm f=0.0015 54 -> 55 0.68061 This state for optimization and/or second-order correction. 291

Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 3.5834 eV 345.99 nm f=0.0036 54 -> 56 0.68081

Excited State 3: Singlet-A 4.2759 eV 289.96 nm f=0.0025 54 -> 57 0.69089

Excited State 4: Singlet-A 4.3605 eV 284.34 nm f=0.0383 52 -> 55 0.40424 52 -> 56 0.14302 53 -> 55 0.49227 53 -> 56 -0.20362

Excited State 5: Singlet-A 4.5329 eV 273.52 nm f=0.1475 52 -> 55 0.44501 52 -> 56 -0.10021 53 -> 55 -0.40927 53 -> 56 -0.27414

Excited State 6: Singlet-A 4.8705 eV 254.56 nm f=0.0162 54 -> 58 0.68450 54 -> 59 -0.10131 54 -> 60 -0.11900

Excited State 7: Singlet-A 5.2392 eV 236.65 nm f=0.0001 54 -> 59 0.67990 54 -> 60 -0.10716 54 -> 61 0.10665

Excited State 8: Singlet-A 5.4315 eV 228.27 nm f=0.0356 53 -> 56 0.15943 54 -> 58 0.14582 54 -> 60 0.61920 54 -> 61 -0.18635

Excited State 9: Singlet-A 5.7248 eV 216.58 nm f=0.2710 51 -> 55 -0.14921 52 -> 55 0.18607 52 -> 56 -0.27715 52 -> 57 -0.22531 53 -> 56 0.38104 53 -> 57 -0.20428 54 -> 61 0.24609

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Spectrum: B3LYP predicted IR spectra of N-Methyl-2-indolyl(CF 3)ring- opened carbene 247

N-Methyl-3-indolyl(CF 3)diazirine (259)

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -2.586206 -2.335955 -0.318409 2 6 0 -3.647512 -1.409241 -0.396001 3 6 0 -3.426090 -0.044133 -0.236780 4 6 0 -2.110909 0.371300 0.006027 5 6 0 -1.028230 -0.546148 0.090294 6 6 0 -1.280860 -1.919582 -0.079386 7 7 0 -1.604727 1.647832 0.193348 8 6 0 -0.248854 1.557085 0.397667 9 6 0 0.155633 0.238923 0.345304 10 6 0 1.531833 -0.256881 0.523126 11 6 0 2.577744 0.105808 -0.509617 12 9 0 3.788730 -0.410367 -0.207380 13 9 0 2.727261 1.454011 -0.606927 14 9 0 2.237970 -0.341032 -1.740821 15 7 0 2.055866 -0.542712 1.892267 293

16 7 0 1.759680 -1.536135 1.240309 17 6 0 -2.384990 2.872102 0.176841 18 1 0 -2.794728 -3.393268 -0.451102 19 1 0 -4.655080 -1.766730 -0.585871 20 1 0 -4.245046 0.665680 -0.300996 21 1 0 -0.472232 -2.641465 -0.027761 22 1 0 0.340814 2.447419 0.565459 23 1 0 -1.719155 3.720126 0.344249 24 1 0 -3.143566 2.860040 0.966892 25 1 0 -2.881734 3.002126 -0.790588 ------

Zero-point correction= 0.176233 (Hartree/Particle) Sum of electronic and zero-point Energies= -887.571715

TD B3LYP of N-Methyl-3-indolyl(CF 3)diazirine (259)

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 2.7294 eV 454.25 nm f=0.0086 61 -> 62 0.69575 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 3.3331 eV 371.98 nm f=0.0013 60 -> 62 0.70533

Excited State 3: Singlet-A 3.9456 eV 314.24 nm f=0.0013 58 -> 62 0.48263 59 -> 62 0.46607

Excited State 4: Singlet-A 4.5595 eV 271.92 nm f=0.1026 60 -> 63 0.18611 60 -> 65 0.17026 61 -> 63 0.61287

Excited State 5: Singlet-A 4.6977 eV 263.93 nm f=0.0029 58 -> 62 -0.46248 59 -> 62 0.48595 60 -> 63 -0.16409

Excited State 6: Singlet-A 4.7854 eV 259.09 nm f=0.0410 58 -> 62 -0.12965 59 -> 62 0.15816 60 -> 63 0.51079 61 -> 63 -0.14738 61 -> 65 -0.39499

Excited State 7: Singlet-A 5.1312 eV 241.63 nm f=0.0123 294

61 -> 64 0.70190

Excited State 8: Singlet-A 5.5805 eV 222.17 nm f=0.0001 60 -> 64 0.67369 61 -> 66 0.18090

Excited State 9: Singlet-A 5.5992 eV 221.43 nm f=0.0212 59 -> 63 0.11624 60 -> 64 -0.17326 61 -> 65 0.20293 61 -> 66 0.60766

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Spectrum: B3LYP predicted IR spectra of N-Methyl-3-indolyl(CF 3)diazirine (259)

N-Methyl-3-indolyl(CF 3)carbene (260a)singlet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------295

1 6 0 2.916099 -2.119800 -0.000602 2 6 0 3.770825 -1.001671 0.001160 3 6 0 3.259191 0.297631 0.001047 4 6 0 1.870107 0.420656 -0.000945 5 6 0 0.997375 -0.681408 -0.002777 6 6 0 1.528131 -1.973037 -0.002529 7 7 0 1.074414 1.590810 -0.001258 8 6 0 -0.218500 1.260357 -0.003949 9 6 0 -0.381068 -0.164561 -0.004632 10 6 0 -1.510914 -0.959631 -0.003056 11 6 0 -2.854282 -0.329249 -0.000169 12 9 0 -3.524706 -0.679424 1.128954 13 9 0 -3.572482 -0.752205 -1.072821 14 9 0 -2.981061 1.070737 -0.046207 15 6 0 1.614232 2.944963 0.002112 16 1 0 3.349223 -3.115555 -0.000361 17 1 0 4.846307 -1.149511 0.002654 18 1 0 3.919128 1.159245 0.002453 19 1 0 0.861226 -2.828889 -0.003742 20 1 0 -0.985695 2.020595 -0.004360 21 1 0 0.789365 3.657742 0.001064 22 1 0 2.230554 3.102967 -0.887535 23 1 0 2.226058 3.100266 0.895343 ------

Zero-point correction= 0.166090 (Hartree/Particle) Sum of electronic and zero-point Energies= -778.055986

TD B3LYP N-Methyl-3-indolyl(CF 3)carbene (260a)singlet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 1.5895 eV 780.03 nm f=0.0016 54 -> 55 0.62671 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 3.6178 eV 342.71 nm f=0.0583 51 -> 55 0.16184 52 -> 55 -0.24508 53 -> 55 0.59751

Excited State 3: Singlet-A 3.7391 eV 331.59 nm f=0.1013 52 -> 55 0.62510 53 -> 55 0.22643

Excited State 4: Singlet-A 3.7479 eV 330.81 nm f=0.0014 54 -> 56 0.69726

Excited State 5: Singlet-A 4.6031 eV 269.35 nm f=0.0004 296

54 -> 58 0.70596

Excited State 6: Singlet-A 4.6377 eV 267.34 nm f=0.0041 54 -> 57 0.69994

Excited State 7: Singlet-A 5.1524 eV 240.63 nm f=0.1238 51 -> 55 0.27593 52 -> 56 0.51426 53 -> 58 0.35605

Excited State 8: Singlet-A 5.2877 eV 234.48 nm f=0.0412 51 -> 55 -0.30971 52 -> 56 0.15568 52 -> 58 0.13938 53 -> 56 -0.24370 53 -> 58 0.16196 54 -> 59 0.48260

Excited State 9: Singlet-A 5.3031 eV 233.80 nm f=0.0746 51 -> 55 0.22505 52 -> 58 -0.16576 53 -> 56 0.39728 54 -> 59 0.45664

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B3LYP predicted IR spectra of N-Methyl-3-indolyl(CF3)carbene (260a)singlet

297

N-Methyl-3-indolyl(CF 3)carbene (260a)triplet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -2.766071 -2.254769 0.003823 2 6 0 -3.712959 -1.212929 0.037856 3 6 0 -3.318815 0.124873 0.035574 4 6 0 -1.946134 0.389707 -0.002534 5 6 0 -0.981297 -0.645600 -0.037031 6 6 0 -1.399542 -1.980910 -0.033624 7 7 0 -1.276919 1.608736 -0.013075 8 6 0 0.075605 1.379216 -0.056208 9 6 0 0.334623 -0.008374 -0.068302 10 6 0 1.560985 -0.642781 -0.118839 11 6 0 2.963563 -0.268626 0.004121 12 9 0 3.774814 -1.033746 -0.770942 13 9 0 3.449127 -0.378486 1.279160 14 9 0 3.177092 1.038287 -0.362604 15 6 0 -1.914382 2.911986 0.018692 16 1 0 -3.107605 -3.285274 0.007067 17 1 0 -4.771259 -1.454313 0.066656 18 1 0 -4.053763 0.923241 0.062255 19 1 0 -0.671603 -2.786101 -0.060025 20 1 0 0.780671 2.196529 -0.075996 21 1 0 -1.144375 3.684410 -0.001046 22 1 0 -2.508550 3.030587 0.931396 23 1 0 -2.567842 3.044521 -0.850480 ------

Zero-point correction= 0.164884 (Hartree/Particle) Sum of electronic and zero-point Energies= -778.043298

TD B3LYP N-Methyl-3-indolyl(CF 3)carbene (260a)triplet

Excitation energies and oscillator strengths:

Excited State 1: ?Spin -A 2.4574 eV 504.54 nm f=0.0011 51B -> 54B 0.20691 298

52B -> 54B 0.84577 53B -> 54B 0.50338 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: ?Spin -A 2.7986 eV 443.02 nm f=0.0007 55A -> 56A -0.29215 52B -> 54B -0.47220 52B -> 55B -0.10050 53B -> 54B 0.80173 53B -> 55B -0.20689

Excited State 3: ?Spin -A 2.8484 eV 435.28 nm f=0.0070 55A -> 56A 0.80502 52B -> 54B -0.15849 52B -> 55B 0.28259 52B -> 56B 0.14341 53B -> 54B 0.31761 53B -> 55B 0.41632

Excited State 4: ?Spin -A 3.2201 eV 385.03 nm f=0.0085 53A -> 56A -0.21184 54A -> 58A -0.18821 55A -> 56A -0.30995 55A -> 58A 0.13465 52B -> 55B -0.20305 52B -> 56B -0.28915 53B -> 55B 0.83845 53B -> 58B 0.12560

Excited State 5: ?Spin -A 3.4879 eV 355.47 nm f=0.1040 53A -> 56A -0.19810 54A -> 56A -0.11143 55A -> 56A -0.25590 55A -> 63A 0.10606 55A -> 65A 0.11069 52B -> 55B 0.88365 52B -> 56B -0.19684

Excited State 6: ?Spin -A 3.9124 eV 316.90 nm f=0.0278 53A -> 56A -0.35610 53A -> 58A 0.14451 54A -> 56A -0.20331 54A -> 58A -0.18010 55A -> 56A 0.23815 55A -> 58A 0.67491 51B -> 55B 0.11712 51B -> 56B 0.13593 52B -> 55B -0.15886 52B -> 56B -0.32984 52B -> 58B -0.21381 53B -> 55B -0.23453 53B -> 58B 0.23492 299

Excited State 7: ?Spin -A 4.0515 eV 306.02 nm f=0.0097 53A -> 56A 0.32913 54A -> 56A 0.37064 54A -> 58A 0.11426 55A -> 56A -0.14641 55A -> 58A 0.58181 52B -> 56B 0.26612 53B -> 56B 0.55397 53B -> 58B -0.16911

Excited State 8: ?Spin -A 4.0725 eV 304.44 nm f=0.0045 55A -> 57A 0.98380 55A -> 60A -0.10171

Excited State 9: ?Spin -A 4.2187 eV 293.89 nm f=0.0081 53A -> 56A -0.32652 54A -> 56A 0.61052 55A -> 56A 0.10497 55A -> 58A -0.32723 55A -> 63A 0.10772 52B -> 56B -0.46863 53B -> 55B -0.13629 53B -> 56B 0.42365

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Spectrum: B3LYP predicted IR spectra of N-Methyl-3-indolyl(CF 3)carbene (260a)triplet

300

N-Methyl-3-indolyl(CF 3)carbene (260b)singlet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 1.265555 2.614065 0.000197 2 6 0 2.602404 2.184136 0.000209 3 6 0 2.915156 0.823459 -0.000021 4 6 0 1.844447 -0.068190 -0.000335 5 6 0 0.491052 0.333747 -0.000364 6 6 0 0.206498 1.703834 -0.000066 7 7 0 1.885636 -1.483296 -0.000441 8 6 0 0.638896 -1.954534 -0.000139 9 6 0 -0.324067 -0.905567 -0.000217 10 6 0 -1.659464 -1.277442 0.000089 11 6 0 3.111232 -2.270317 0.000192 12 6 0 -2.671795 -0.179092 -0.000048 13 9 0 -3.949072 -0.638251 -0.002277 14 9 0 -2.579176 0.635140 -1.104385 15 9 0 -2.581038 0.631236 1.107160 16 1 0 1.050448 3.678328 0.000422 17 1 0 3.403796 2.916402 0.000449 18 1 0 3.946877 0.486350 0.000153 19 1 0 -0.817352 2.055116 -0.000088 20 1 0 0.422371 -3.014715 -0.000055 21 1 0 2.852719 -3.329567 -0.004606 22 1 0 3.700466 -2.046624 0.894242 23 1 0 3.705316 -2.039948 -0.888888 ------

Zero-point correction= 0.166252 (Hartree/Particle) Sum of electronic and zero-point Energies= -778.054910

TD B3LYP N-Methyl-3-indolyl(CF 3)carbene (260b)singlet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 1.6189 eV 765.88 nm f=0.0010 54 -> 55 0.62628 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 3.6810 eV 336.82 nm f=0.0011 301

54 -> 56 0.69792

Excited State 3: Singlet-A 3.7709 eV 328.79 nm f=0.0202 51 -> 55 -0.10180 52 -> 55 0.59888 53 -> 55 -0.29219

Excited State 4: Singlet-A 3.8223 eV 324.37 nm f=0.1458 51 -> 55 0.15800 52 -> 55 0.31295 52 -> 56 0.10627 53 -> 55 0.56134

Excited State 5: Singlet-A 4.5791 eV 270.76 nm f=0.0042 54 -> 57 0.69649

Excited State 6: Singlet-A 4.5818 eV 270.60 nm f=0.0002 54 -> 58 0.70386

Excited State 7: Singlet-A 5.1286 eV 241.75 nm f=0.1390 51 -> 55 0.28650 52 -> 56 0.45539 53 -> 56 0.11704 53 -> 58 0.27553 54 -> 59 -0.25314 54 -> 60 -0.12062

Excited State 8: Singlet-A 5.2143 eV 237.78 nm f=0.0072 51 -> 55 -0.21450 52 -> 56 0.28987 53 -> 56 0.15057 53 -> 58 0.24275 54 -> 59 0.48217 54 -> 60 0.18354

Excited State 9: Singlet-A 5.3179 eV 233.15 nm f=0.1221 51 -> 55 0.18517 51 -> 56 -0.12493 52 -> 56 -0.18143 52 -> 58 -0.19839 53 -> 56 0.54143 53 -> 58 -0.15666 54 -> 59 0.11039

********************************************************************** 302

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Spectrum: B3LYP predicted IR spectra of N-Methyl-3-indolyl(CF 3)carbene (260b)singlet

N-Methyl-3-indolyl(CF 3)carbene (260b)triplet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -1.341823 2.612343 -0.000214 2 6 0 -2.680793 2.177954 0.000136 3 6 0 -2.999930 0.820734 0.000383 4 6 0 -1.938285 -0.089671 0.000342 5 6 0 -0.585022 0.330307 -0.000173 6 6 0 -0.288824 1.698656 -0.000382 7 7 0 -1.968017 -1.479426 0.000707 8 6 0 -0.681244 -1.953695 0.000003 9 6 0 0.237524 -0.887132 -0.000386 10 6 0 1.614188 -1.010080 -0.000862 11 6 0 -3.172270 -2.288551 -0.000538 303

12 6 0 2.791874 -0.154195 -0.000016 13 9 0 3.934071 -0.886690 -0.001471 14 9 0 2.859367 0.676254 1.090817 15 9 0 2.858619 0.679426 -1.088490 16 1 0 -1.126419 3.676326 -0.000424 17 1 0 -3.480961 2.911988 0.000166 18 1 0 -4.033874 0.490125 0.000535 19 1 0 0.739131 2.044211 -0.000765 20 1 0 -0.479173 -3.014861 0.000039 21 1 0 -2.891983 -3.342830 0.005849 22 1 0 -3.772289 -2.089284 -0.895219 23 1 0 -3.779197 -2.080627 0.887401 ------

Zero-point correction= 0.164802 (Hartree/Particle)

Sum of electronic and zero-point Energies= -778.042566

TD B3LYP N-Methyl-3-indolyl(CF 3)carbene (260b)triplet

Excitation energies and oscillator strengths:

Excited State 1: ?Spin -A 2.4869 eV 498.54 nm f=0.0005 51B -> 54B -0.21910 52B -> 54B 0.91109 53B -> 54B 0.36943 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: ?Spin -A 2.8223 eV 439.31 nm f=0.0000 52B -> 54B -0.36272 53B -> 54B 0.92910

Excited State 3: ?Spin -A 2.8441 eV 435.93 nm f=0.0084 55A -> 56A 0.85621 51B -> 55B -0.10982 52B -> 55B 0.35842 52B -> 56B -0.15595 53B -> 55B 0.41937

Excited State 4: ?Spin -A 3.2084 eV 386.44 nm f=0.0098 53A -> 56A 0.19645 54A -> 58A 0.18757 55A -> 56A -0.28968 55A -> 58A 0.12736 52B -> 55B -0.15269 52B -> 56B 0.28069 53B -> 55B 0.86577 53B -> 58B 0.13021

304

Excited State 5: ?Spin -A 3.4740 eV 356.89 nm f=0.0986 53A -> 56A 0.21008 55A -> 56A -0.28009 55A -> 62A -0.11020 55A -> 65A -0.10976 52B -> 55B 0.86981 52B -> 56B 0.21809

Excited State 6: ?Spin -A 3.9173 eV 316.51 nm f=0.0317 53A -> 56A 0.35341 53A -> 58A -0.14020 54A -> 56A 0.17203 54A -> 58A 0.18468 55A -> 56A 0.23247 55A -> 58A 0.69817 51B -> 55B -0.12948 51B -> 56B 0.13542 52B -> 55B -0.17224 52B -> 56B 0.32643 52B -> 58B -0.19288 53B -> 55B -0.21212 53B -> 58B 0.25564

Excited State 7: ?Spin -A 4.0215 eV 308.30 nm f=0.0045 55A -> 57A 0.98498 55A -> 59A -0.11160

Excited State 8: ?Spin -A 4.0724 eV 304.45 nm f=0.0092 53A -> 56A -0.35664 54A -> 56A -0.36663 54A -> 58A -0.12614 55A -> 56A -0.15485 55A -> 58A 0.55645 52B -> 56B -0.34004 53B -> 56B -0.52062 53B -> 58B -0.17560

Excited State 9: ?Spin -A 4.2224 eV 293.63 nm f=0.0090 53A -> 56A -0.30173 54A -> 56A 0.62817 55A -> 56A -0.10627 55A -> 58A 0.32950 55A -> 62A 0.12005 52B -> 56B -0.41126 53B -> 55B 0.13172 53B -> 56B 0.47486

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Spectrum: B3LYP predicted IR spectra of N-Methyl-3-indolyl(CF 3)carbene (260b)triplet

N-Methyl-3-indolyl(CF 3)methylenecyclopropene 265a

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -3.546388 -1.388787 0.000145 2 6 0 -3.869123 0.017791 -0.000318 3 6 0 -2.908654 0.982614 -0.000495 4 6 0 -1.481140 0.653909 -0.000309 5 6 0 -1.173101 -0.803474 -0.000050 6 6 0 -2.242190 -1.775561 0.000256 7 6 0 0.120771 -1.217279 -0.000124 8 7 0 -0.498213 1.500838 0.000211 9 6 0 1.520428 -0.946033 -0.000377 306

10 6 0 1.139777 -2.217795 0.000277 11 6 0 2.668528 0.003603 -0.000194 12 9 0 3.839419 -0.684412 -0.002181 13 9 0 2.658697 0.785418 1.093799 14 9 0 2.656897 0.788746 -1.091654 15 6 0 -0.786197 2.924759 0.000628 16 1 0 -4.345061 -2.123335 0.000389 17 1 0 -4.916889 0.309586 -0.000563 18 1 0 -3.198532 2.027039 -0.000902 19 1 0 -1.977770 -2.830188 0.000559 20 1 0 1.426837 -3.259719 0.000768 21 1 0 0.158360 3.475434 0.003320 22 1 0 -1.357723 3.242046 0.887264 23 1 0 -1.353117 3.243011 -0.888623 ------

Zero-point correction= 0.162879 (Hartree/Particle) Sum of electronic and zero-point Energies= -778.005083

TD B3LYP of methylenecyclopropene 265a

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 2.3995 eV 516.70 nm f=0.0061 54 -> 55 0.68778 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.9463 eV 420.81 nm f=0.1706 54 -> 56 0.60780

Excited State 3: Singlet-A 3.3191 eV 373.54 nm f=0.0001 53 -> 56 0.68656

Excited State 4: Singlet-A 3.5175 eV 352.48 nm f=0.0001 53 -> 55 0.70440

Excited State 5: Singlet-A 4.4016 eV 281.68 nm f=0.0015 54 -> 57 0.69519 54 -> 58 -0.10699

Excited State 6: Singlet-A 4.7019 eV 263.69 nm f=0.0038 52 -> 55 0.69143

Excited State 7: Singlet-A 4.7997 eV 258.31 nm f=0.0397 52 -> 56 0.57980 54 -> 60 -0.12998 54 -> 62 0.32755 307

Excited State 8: Singlet-A 4.8250 eV 256.96 nm f=0.0019 54 -> 57 0.10724 54 -> 58 0.69089

Excited State 9: Singlet-A 4.9558 eV 250.18 nm f=0.0214 51 -> 56 0.43703 52 -> 56 0.10515 54 -> 60 0.51519 54 -> 62 0.13849

********************************************************************** 500 450 400 350 300 250 200 150 100 50 0 1900 1700 1500 1300 1100 900 700 500

Spectrum: B3LYP predicted IR spectra of methylenecyclopropene 265a

Bicyclic intermediate 262

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -3.098164 -1.768413 0.101879 2 6 0 -3.496351 -0.568217 0.710134 3 6 0 -2.699604 0.578641 0.670733 4 6 0 -1.482383 0.525175 -0.023065 5 6 0 -1.075069 -0.706692 -0.634047 308

6 6 0 -1.875123 -1.843709 -0.570141 7 6 0 0.251339 -0.398001 -1.118961 8 7 0 -0.533727 1.530328 -0.172471 9 6 0 -0.802862 2.929057 0.101107 10 6 0 0.482598 1.081255 -1.105317 11 6 0 1.452291 -0.011347 -0.721824 12 6 0 2.509095 -0.404228 0.234837 13 9 0 3.758740 -0.089871 -0.198812 14 9 0 2.503932 -1.738251 0.473051 15 9 0 2.343993 0.231827 1.424988 16 1 0 -3.738304 -2.642569 0.160198 17 1 0 -4.453096 -0.524002 1.222614 18 1 0 -3.032936 1.496885 1.143004 19 1 0 -1.549772 -2.767733 -1.037117 20 1 0 -1.597526 3.334346 -0.542382 21 1 0 0.111913 3.500650 -0.066616 22 1 0 -1.096015 3.068295 1.147019 23 1 0 0.637231 1.707356 -1.984480 ------

Zero-point correction= 0.165695 (Hartree/Particle) Sum of electronic and zero-point Energies= - 778.031579

TD B3LYP of bicyclic intermediate 262

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 3.1666 eV 391.54 nm f=0.0681 54 -> 55 0.66592 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 4.2674 eV 290.54 nm f=0.0506 52 -> 55 0.19288 53 -> 55 0.62840 53 -> 56 0.10143 54 -> 57 0.15717

Excited State 3: Singlet-A 4.5909 eV 270.07 nm f=0.0202 53 -> 57 0.18831 54 -> 56 0.66006

Excited State 4: Singlet-A 4.8312 eV 256.63 nm f=0.0077 51 -> 55 -0.10330 52 -> 55 0.63141 53 -> 55 -0.16424

Excited State 5: Singlet-A 4.9866 eV 248.64 nm f=0.0497 54 -> 57 0.45312 54 -> 58 0.51745 309

Excited State 6: Singlet-A 5.1802 eV 239.34 nm f=0.1259 51 -> 55 0.13069 53 -> 56 0.22737 54 -> 57 -0.41356 54 -> 58 0.45119

Excited State 7: Singlet-A 5.4589 eV 227.12 nm f=0.0139 54 -> 59 0.69653

Excited State 8: Singlet-A 5.5352 eV 223.99 nm f=0.0011 51 -> 55 -0.10389 54 -> 60 0.68156

Excited State 9: Singlet-A 5.8232 eV 212.91 nm f=0.0488 51 -> 55 0.41262 53 -> 57 -0.21063 54 -> 60 0.13641 54 -> 61 0.42744 54 -> 63 0.11059

**********************************************************************

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Spectrum: B3LYP predicted IR spectra of bicyclic intermediate 262

310

Ring-opened carbene 264 singlet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.377241 -1.687394 0.000044 2 6 0 3.830199 -0.352485 -0.000564 3 6 0 2.936730 0.706633 -0.000573 4 6 0 1.549668 0.440508 0.000036 5 6 0 1.054020 -0.902672 0.000360 6 6 0 2.020111 -1.946168 0.000480 7 7 0 0.616789 1.473243 0.000297 8 6 0 -0.705100 1.194071 0.000121 9 6 0 -1.173384 -0.109620 -0.000119 10 6 0 -0.342591 -1.251708 0.000397 11 6 0 1.058248 2.872890 0.000370 12 6 0 -2.672829 -0.315096 -0.000213 13 9 0 -3.357269 0.875172 -0.002920 14 9 0 -3.098292 -0.994274 1.088709 15 9 0 -3.097595 -0.998964 -1.086282 16 1 0 4.095254 -2.501646 0.000099 17 1 0 4.896273 -0.143768 -0.001072 18 1 0 3.318195 1.720898 -0.001196 19 1 0 1.631910 -2.959573 0.000822 20 1 0 -1.363568 2.055911 0.000355 21 1 0 0.180326 3.517670 0.002468 22 1 0 1.652711 3.083942 -0.892534 23 1 0 1.655910 3.082721 0.891385 ------

Zero-point correction= 0.167436 (Hartree/Particle)

Sum of electonic and zero-point Energies= -778.071567

TD B3LYP of ring-opened carbene 264 singlet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 1.4598 eV 849.34 nm f=0.0012 54 -> 55 0.64594 This state for optimization and/or second-order correction. 311

Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.5004 eV 495.87 nm f=0.0001 54 -> 56 0.70021

Excited State 3: Singlet-A 3.5300 eV 351.23 nm f=0.0021 54 -> 58 0.69734

Excited State 4: Singlet-A 3.8400 eV 322.87 nm f=0.0042 54 -> 57 0.70132

Excited State 5: Singlet-A 4.1267 eV 300.45 nm f=0.0536 52 -> 56 -0.15883 53 -> 55 0.63709 54 -> 59 -0.13689

Excited State 6: Singlet-A 4.4256 eV 280.15 nm f=0.0274 53 -> 55 0.11479 54 -> 59 0.67395

Excited State 7: Singlet-A 4.6042 eV 269.29 nm f=0.0164 52 -> 55 0.51695 53 -> 56 0.38964 54 -> 60 0.25307

Excited State 8: Singlet-A 4.6485 eV 266.72 nm f=0.0129 52 -> 55 -0.18499 53 -> 56 -0.18093 54 -> 59 -0.10961 54 -> 60 0.62850 54 -> 61 0.11494

Excited State 9: Singlet-A 4.7859 eV 259.06 nm f=0.0065 54 -> 60 -0.13051 54 -> 61 0.68101

**********************************************************************

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Spectrum: B3LYP predicted IR spectra of ring-opened carbene 264 singlet

Ring-opened carbene 264 triplet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.413066 -1.688702 -0.000004 2 6 0 3.860576 -0.367956 -0.000224 3 6 0 2.940635 0.694377 -0.000205 4 6 0 1.567542 0.441368 0.000099 5 6 0 1.094955 -0.919248 0.000172 6 6 0 2.045553 -1.962873 0.000152 7 7 0 0.616614 1.484720 0.000326 8 6 0 -0.743511 1.231024 -0.000251 9 6 0 -1.229900 -0.057199 -0.000302 10 6 0 -0.300985 -1.098881 0.000115 11 6 0 1.076589 2.867380 0.000144 12 6 0 -2.706524 -0.320269 -0.000110 13 9 0 -3.433894 0.827252 -0.003868 14 9 0 -3.097416 -1.030305 1.089035 313

15 9 0 -3.096479 -1.037049 -1.085063 16 1 0 4.126497 -2.507135 0.000000 17 1 0 4.923432 -0.148104 -0.000426 18 1 0 3.314366 1.711033 -0.000458 19 1 0 1.685386 -2.986394 0.000231 20 1 0 -1.393161 2.095307 -0.000558 21 1 0 0.211476 3.530367 0.001391 22 1 0 1.677951 3.079632 -0.891491 23 1 0 1.679883 3.079035 0.890577 ------

Zero-point correction= 0.165501 (Hartree/Particle) Sum of electronic and zero-point Energies= -778.043462

TD B3LYP Ring-opened carbene 264 triplet

Excitation energies and oscillator strengths:

Excited State 1: ?Spin -A 1.7132 eV 723.71 nm f=0.0035 55A -> 56A 1.01223 52B -> 55B 0.11707 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: ?Spin -A 2.6639 eV 465.43 nm f=0.0003 51B -> 54B 0.19298 53B -> 54B 0.98566

Excited State 3: ?Spin -A 2.7289 eV 454.34 nm f=0.0433 55A -> 57A 0.96726 52B -> 55B -0.17211 53B -> 55B 0.16518 53B -> 56B -0.14653

Excited State 4: ?Spin -A 3.1317 eV 395.90 nm f=0.0048 55A -> 58A 0.99293

Excited State 5: ?Spin -A 3.3866 eV 366.10 nm f=0.0003 51B -> 54B 0.11749 52B -> 54B 0.99013

Excited State 6: ?Spin -A 3.4846 eV 355.80 nm f=0.0123 51A -> 57A -0.11175 54A -> 57A -0.22913 55A -> 57A -0.10996 55A -> 61A -0.33134 314

55A -> 65A 0.18710 53B -> 55B 0.90421 53B -> 58B -0.10646

Excited State 7: ?Spin -A 3.6611 eV 338.65 nm f=0.0021 55A -> 59A 0.96025 55A -> 60A 0.25342

Excited State 8: ?Spin -A 3.7688 eV 328.97 nm f=0.0334 52A -> 56A -0.24998 54A -> 57A -0.28598 55A -> 61A 0.71177 55A -> 65A -0.26295 51B -> 55B -0.22811 52B -> 55B -0.24277 52B -> 56B 0.45579 53B -> 55B 0.18892 53B -> 58B -0.20299

Excited State 9: ?Spin -A 3.8134 eV 325.13 nm f=0.0004 55A -> 59A -0.26463 55A -> 60A 0.94490 55A -> 62A -0.15205

******************************************************************** **

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Spectrum: B3LYP predicted IR spectra of Ring-opened carbene 264 triplet

315

Spiro product 263

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.170980 -1.778656 0.173465 2 6 0 3.806763 -0.696208 -0.451616 3 6 0 3.152990 0.527783 -0.702717 4 6 0 1.832711 0.576346 -0.281388 5 6 0 1.202190 -0.488937 0.374788 6 6 0 1.829783 -1.697338 0.605504 7 7 0 0.687006 1.420969 -0.308667 8 6 0 -0.031486 0.371106 0.496688 9 6 0 -1.009451 0.613923 1.590636 10 6 0 -1.489818 0.114069 0.483764 11 6 0 0.730342 2.810689 0.123199 12 6 0 -2.667105 -0.399080 -0.254286 13 9 0 -3.798835 -0.308213 0.484563 14 9 0 -2.504393 -1.701868 -0.587861 15 9 0 -2.872024 0.289194 -1.400002 16 1 0 3.728097 -2.696645 0.334142 17 1 0 4.843516 -0.806614 -0.757578 18 1 0 3.662022 1.350717 -1.193921 19 1 0 1.348056 -2.535888 1.099719 20 1 0 -1.184135 0.955827 2.600560 21 1 0 1.309938 3.393876 -0.597920 22 1 0 1.179239 2.941838 1.122149 23 1 0 -0.285899 3.215922 0.135001 ------Zero-point correction= 0.164138 (Hartree/Particle)

Sum of electronic and zero-point Energies= -778.009960

TD-B3LYPSpiro product 263

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 3.5984 eV 344.55 nm f=0.0215 54 -> 55 0.69741 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density. 316

Excited State 2: Singlet-A 4.4231 eV 280.31 nm f=0.0163 53 -> 57 -0.18355 54 -> 56 0.65841

Excited State 3: Singlet-A 4.6417 eV 267.11 nm f=0.0044 53 -> 55 0.67454 54 -> 57 -0.12117

Excited State 4: Singlet-A 5.0090 eV 247.52 nm f=0.0785 53 -> 56 0.11899 54 -> 57 0.57630 54 -> 58 0.31983

Excited State 5: Singlet-A 5.2342 eV 236.87 nm f=0.0536 53 -> 56 -0.18191 54 -> 57 -0.24847 54 -> 58 0.59267

Excited State 6: Singlet-A 5.4409 eV 227.87 nm f=0.0092 54 -> 58 0.11047 54 -> 59 0.68940

Excited State 7: Singlet-A 5.4811 eV 226.20 nm f=0.0036 52 -> 55 0.67139 53 -> 55 -0.10549

Excited State 8: Singlet-A 5.5785 eV 222.26 nm f=0.0033 54 -> 60 0.68746

Excited State 9: Singlet-A 5.7711 eV 214.84 nm f=0.0038 54 -> 61 0.67765 54 -> 62 -0.10981

******************************************************************** **

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Spectrum: B3LYP predicted IR spectra of spiro product 263

Benzothiazolyl(CF 3)diazirine (277b)

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.964442 -1.421472 0.000259 2 6 0 4.405816 -0.083954 -0.000098 3 6 0 3.499371 0.973905 -0.000325 4 6 0 2.134608 0.667110 -0.000169 5 6 0 1.678728 -0.675495 0.000184 6 6 0 2.608598 -1.727106 0.000398 7 16 0 0.761954 1.754267 -0.000216 8 6 0 -0.293452 0.317228 0.000086 9 7 0 0.303138 -0.830003 0.000096 10 6 0 -1.756337 0.487668 0.000176 11 6 0 -2.653082 -0.739573 -0.000122 12 9 0 -3.952004 -0.358677 -0.000862 13 9 0 -2.453446 -1.504206 1.090580 14 9 0 -2.452208 -1.504275 -1.090696 15 7 0 -2.313635 1.721284 0.612996 16 7 0 -2.313677 1.721682 -0.611698 318

17 1 0 4.695630 -2.223828 0.000414 18 1 0 5.470391 0.129119 -0.000230 19 1 0 3.845718 2.002234 -0.000643 20 1 0 2.252992 -2.751995 0.000620

------

Zero-point correction= 0.120913 (Hartree/Particle) Sum of electronic and zero-point Energies= -1207.186626

TD B3LYP of benzothiazolyl(CF 3)diazirine (277b)

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 3.0571 eV 405.56 nm f=0.0175 58 -> 62 -0.13671 60 -> 62 -0.32204 61 -> 62 0.58011 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 3.3568 eV 369.35 nm f=0.0192 60 -> 62 0.59096 61 -> 62 0.35900

Excited State 3: Singlet-A 4.4010 eV 281.72 nm f=0.0000 59 -> 62 0.70073

Excited State 4: Singlet-A 4.4739 eV 277.13 nm f=0.0162 57 -> 62 0.24164 58 -> 62 0.19390 60 -> 63 0.49771 61 -> 63 0.26214 61 -> 64 0.21473

Excited State 5: Singlet-A 4.5541 eV 272.24 nm f=0.0133 55 -> 62 -0.10643 57 -> 62 0.31088 58 -> 62 0.48427 60 -> 62 -0.10630 60 -> 63 -0.28746 61 -> 62 0.13640 61 -> 64 -0.10118

Excited State 6: Singlet-A 4.7630 eV 260.31 nm f=0.3516 60 -> 63 -0.27216 60 -> 64 -0.15760 61 -> 63 0.56769

319

Excited State 7: Singlet-A 5.1257 eV 241.89 nm f=0.0129 57 -> 62 0.54510 58 -> 62 -0.41942

Excited State 8: Singlet-A 5.2165 eV 237.68 nm f=0.0002 59 -> 63 0.68051

Excited State 9: Singlet-A 5.3469 eV 231.88 nm f=0.0000 59 -> 63 -0.10362 60 -> 65 0.51522 61 -> 65 0.45120

************************************************************

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Spectrum: B3LYP predicted IR of Benzothiazolyl((CF 3)diazirine (277b)

Benzothiazolyl(CF 3)diazirine (277a)

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------320

1 6 0 -4.328717 0.790840 0.048341 2 6 0 -4.372814 -0.616489 0.008754 3 6 0 -3.203829 -1.373695 -0.026841 4 6 0 -1.982863 -0.691565 -0.022015 5 6 0 -1.925373 0.723034 0.016547 6 6 0 -3.115100 1.468060 0.052502 7 16 0 -0.356187 -1.340107 -0.064138 8 6 0 0.251203 0.325546 -0.019497 9 7 0 -0.650300 1.259435 0.016953 10 6 0 1.690397 0.666830 -0.030147 11 7 0 2.074230 1.937956 -0.698374 12 7 0 2.062591 1.994578 0.521202 13 6 0 2.754277 -0.407976 0.038402 14 9 0 2.661942 -1.123255 1.184430 15 9 0 3.987103 0.128112 -0.014972 16 9 0 2.638699 -1.286320 -0.986759 17 1 0 -5.257290 1.352464 0.076025 18 1 0 -5.333346 -1.122596 0.005779 19 1 0 -3.244238 -2.457628 -0.057380 20 1 0 -3.064552 2.551344 0.082759 ------

Zero-point correction= 0.120856 (Hartree/Particle) Sum of electronic and zero-point Energies= -1207.186336

TD B3LYP of benzothiazolyl(CF 3)diazirine (277a)

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 3.2521 eV 381.25 nm f=0.0252 58 -> 62 -0.16458 60 -> 62 0.38935 61 -> 62 0.52899 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 3.5709 eV 347.21 nm f=0.0043 60 -> 62 0.56574 61 -> 62 -0.41386

Excited State 3: Singlet-A 4.4994 eV 275.56 nm f=0.0179 59 -> 62 0.43704 60 -> 63 -0.39525 61 -> 63 0.30853 61 -> 64 -0.17687

Excited State 4: Singlet-A 4.5038 eV 275.29 nm f=0.0115 59 -> 62 0.54520 60 -> 63 0.35186 61 -> 63 -0.19270 321

61 -> 64 0.14725

Excited State 5: Singlet-A 4.6819 eV 264.82 nm f=0.3010 58 -> 62 -0.20195 60 -> 63 0.32934 60 -> 64 -0.12011 61 -> 62 -0.11855 61 -> 63 0.48595

Excited State 6: Singlet-A 4.7250 eV 262.40 nm f=0.0079 55 -> 62 0.11342 57 -> 62 -0.18597 58 -> 62 0.58612 60 -> 62 0.11866 60 -> 63 0.12491 61 -> 62 0.11948 61 -> 63 0.19918

Excited State 7: Singlet-A 5.2315 eV 237.00 nm f=0.0005 59 -> 63 0.68299

Excited State 8: Singlet-A 5.3341 eV 232.44 nm f=0.0099 57 -> 62 0.61142 58 -> 62 0.19604 60 -> 66 -0.10860 61 -> 64 0.22637

Excited State 9: Singlet-A 5.3729 eV 230.76 nm f=0.0000 60 -> 65 0.55116 61 -> 65 -0.40634

**********************************************************************

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Spectrum: B3LYP predicted IR of benzothiazolyl(CF 3)diazirine (277a) 322

Benzothiazolyl(CF 3)carbene (278b) singlet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -3.530690 -1.536438 0.005730 2 6 0 -4.074260 -0.220913 -0.003171 3 6 0 -3.269055 0.905322 -0.008903 4 6 0 -1.873804 0.722582 -0.004406 5 6 0 -1.309938 -0.606236 0.003544 6 6 0 -2.169667 -1.738903 0.009627 7 16 0 -0.608553 1.879452 -0.006009 8 6 0 0.598074 0.540618 -0.008012 9 7 0 0.032302 -0.671854 -0.001748 10 6 0 1.938262 0.937364 -0.002721 11 6 0 2.938255 -0.184006 -0.007802 12 9 0 4.207018 0.270802 -0.159644 13 9 0 2.754893 -1.093788 -1.004506 14 9 0 2.906930 -0.840297 1.186543 15 1 0 -4.206538 -2.385526 0.008815 16 1 0 -5.153398 -0.099140 -0.005273 17 1 0 -3.701968 1.899909 -0.015309 18 1 0 -1.729999 -2.730299 0.015290 ------

Zero-point correction= 0.109598 (Hartree/Particle) Sum of electronic and zero-point Energies= -1097.647714

TD B3LYP of benzothiazolyl(CF 3)carbene (278b) singlet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 0.9788 eV 1266.65 nm f=0.0006 54 -> 55 0.58579 323

This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.6417 eV 469.34 nm f=0.0239 53 -> 55 0.64915

Excited State 3: Singlet-A 3.0320 eV 408.92 nm f=0.0000 51 -> 55 0.68446

Excited State 4: Singlet-A 3.6677 eV 338.05 nm f=0.4425 52 -> 55 0.59817 53 -> 56 0.10615 53 -> 57 -0.10520

Excited State 5: Singlet-A 4.4516 eV 278.51 nm f=0.0080 50 -> 55 0.65952 53 -> 56 -0.10424

Excited State 6: Singlet-A 4.4716 eV 277.27 nm f=0.0034 54 -> 56 -0.34191 54 -> 57 0.58599

Excited State 7: Singlet-A 4.5357 eV 273.35 nm f=0.0005 54 -> 56 0.61743 54 -> 57 0.32601

Excited State 8: Singlet-A 4.8674 eV 254.72 nm f=0.0019 49 -> 55 0.69279

Excited State 9: Singlet-A 4.9897 eV 248.48 nm f=0.0071 54 -> 58 0.67182 54 -> 59 0.18240

********************************************************************** 600

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324

Spectrum: B3LYP predicted IR of benzothiazolyl(CF 3)carbene (278b) singlet

Benzothiazolyl(CF 3)carbene (278b) triplet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -3.713290 -1.458288 0.000843 2 6 0 -4.194462 -0.130908 0.002825 3 6 0 -3.321448 0.955940 0.002413 4 6 0 -1.948292 0.698153 0.000064 5 6 0 -1.446176 -0.639336 -0.001593 6 6 0 -2.353173 -1.722238 -0.001295 7 16 0 -0.618404 1.830081 -0.001298 8 6 0 0.507694 0.423781 -0.003785 9 7 0 -0.089089 -0.770866 -0.003743 10 6 0 1.866143 0.628574 -0.005545 11 6 0 3.092933 -0.187083 0.000411 12 9 0 4.188617 0.610528 -0.039659 13 9 0 3.163377 -1.022134 -1.066373 14 9 0 3.195946 -0.955329 1.114276 15 1 0 -4.421602 -2.280813 0.001018 16 1 0 -5.265125 0.049187 0.004665 17 1 0 -3.702115 1.971978 0.003918 18 1 0 -1.964102 -2.734742 -0.002849 ------

Zero-point correction= 0.109271 (Hartree/Particle) Sum of electronic and zero-point Energies= -1097.654510

TD B3LYP benzothiazolyl(CF 3)carbene (278b) triplet

Excitation energies and oscillator strengths:

325

Excited State 1: ?Spin -A 2.1898 eV 566.20 nm f=0.0111 54A -> 56A -0.15395 53B -> 54B 0.99084 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: ?Spin -A 2.3510 eV 527.36 nm f=0.0000 50B -> 55B 0.11623 52B -> 55B 0.17941 53B -> 55B 0.97544

Excited State 3: ?Spin -A 2.7774 eV 446.40 nm f=0.0003 48B -> 55B -0.16211 52B -> 55B 0.97372 53B -> 55B -0.17732

Excited State 4: ?Spin -A 2.8842 eV 429.87 nm f=0.0003 51B -> 54B 0.99468 51B -> 61B 0.11046

Excited State 5: ?Spin -A 2.9000 eV 427.54 nm f=0.0786 55A -> 56A -0.42349 55A -> 57A -0.12690 52B -> 54B 0.90856 53B -> 56B -0.12989

Excited State 6: ?Spin -A 3.3215 eV 373.28 nm f=0.0004 51B -> 55B 0.99247

Excited State 7: ?Spin -A 3.7890 eV 327.22 nm f=0.0137 50A -> 56A -0.13010 54A -> 56A 0.23711 54A -> 57A -0.43461 55A -> 56A 0.15152 55A -> 60A 0.17167 50B -> 54B 0.75338 50B -> 56B -0.11810 52B -> 54B 0.12975 52B -> 57B 0.11170 53B -> 56B 0.38705 53B -> 57B 0.12549

Excited State 8: ?Spin -A 3.9567 eV 313.35 nm f=0.0382 50A -> 57A 0.12450 52A -> 57A -0.13948 54A -> 56A 0.21032 54A -> 57A -0.31903 55A -> 56A 0.12761 55A -> 57A 0.62440 50B -> 54B -0.49107 50B -> 56B -0.14958 52B -> 54B 0.17203 52B -> 56B -0.16963 326

52B -> 57B 0.19052 53B -> 56B 0.35223

Excited State 9: ?Spin -A 4.1814 eV 296.51 nm f=0.0000 50B -> 55B 0.98650 53B -> 55B -0.11923

*******************************************************

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Spectrum: B3LYP predicted IR of benzothiazolyl(CF 3)carbene (278b) triplet

Benzothiazolyl(CF 3)carbene (278a) singlet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -4.111319 -0.715018 0.011524 2 6 0 -4.041151 0.707119 0.021462 3 6 0 -2.833409 1.384405 0.013425 4 6 0 -1.647303 0.626394 -0.004076 5 6 0 -1.705335 -0.813108 -0.014468 6 6 0 -2.965388 -1.475197 -0.006231 7 16 0 -0.018667 1.154367 -0.020065 8 6 0 0.526616 -0.614062 -0.035274 327

9 7 0 -0.525762 -1.447904 -0.032135 10 6 0 1.827803 -1.093817 -0.042511 11 6 0 2.975060 -0.143898 -0.000019 12 9 0 3.887388 -0.465539 -0.945136 13 9 0 2.740475 1.209232 -0.185349 14 9 0 3.557066 -0.243980 1.221797 15 1 0 -5.084408 -1.195149 0.018244 16 1 0 -4.965488 1.277206 0.035880 17 1 0 -2.802307 2.468602 0.021182 18 1 0 -2.986597 -2.559536 -0.014109 ------

Zero-point correction= 0.109620 (Hartree/Particle) Sum of electronic and zero-point Energies= -1097.648369

TD B3LYP of benzothiazolyl(CF 3)carbene (278a) singlet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 0.9214 eV 1345.58 nm f=0.0007 54 -> 55 0.59642 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.6009 eV 476.70 nm f=0.0220 53 -> 55 0.64832

Excited State 3: Singlet-A 3.0159 eV 411.11 nm f=0.0004 51 -> 55 0.68176

Excited State 4: Singlet-A 3.6561 eV 339.12 nm f=0.3977 52 -> 55 0.59243 53 -> 57 -0.10967 54 -> 58 -0.11035

Excited State 5: Singlet-A 4.3980 eV 281.91 nm f=0.0056 50 -> 55 0.65832 53 -> 56 0.11462

Excited State 6: Singlet-A 4.4342 eV 279.61 nm f=0.0001 54 -> 56 0.67875 54 -> 57 0.18776

Excited State 7: Singlet-A 4.4733 eV 277.16 nm f=0.0019 54 -> 56 -0.19268 54 -> 57 0.65018 54 -> 62 0.10024

Excited State 8: Singlet-A 4.8793 eV 254.10 nm f=0.0006 49 -> 55 0.69877

328

Excited State 9: Singlet-A 5.1554 eV 240.49 nm f=0.1280 48 -> 55 0.13447 54 -> 58 0.65151 54 -> 59 0.10039

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Spectrum: B3LYP predicted IR of benzothiazolyl(CF 3)carbene (278a) singlet

Benzothiazolyl(CF 3)carbene (278a) triplet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -4.156201 -0.789012 0.013827 2 6 0 -4.146637 0.623227 0.017949 3 6 0 -2.950805 1.339722 0.009368 4 6 0 -1.751664 0.622246 -0.003696 5 6 0 -1.745161 -0.806573 -0.008270 6 6 0 -2.972219 -1.507620 0.000905 7 16 0 -0.115783 1.229034 -0.018496 8 6 0 0.462048 -0.497508 -0.022813 9 7 0 -0.521461 -1.401441 -0.019002 329

10 6 0 1.794502 -0.815947 -0.037156 11 6 0 3.100376 -0.146931 0.004705 12 9 0 3.945905 -0.639362 -0.930532 13 9 0 2.986769 1.194119 -0.218659 14 9 0 3.712354 -0.295395 1.206980 15 1 0 -5.105876 -1.314590 0.021222 16 1 0 -5.088149 1.163787 0.028092 17 1 0 -2.955534 2.424689 0.012640 18 1 0 -2.958393 -2.592226 -0.002019 ------

Zero-point correction= 0.109130 (Hartree/Particle) Sum of electronic and zero-point Energies= -1097.655637

TD B3LYP of benzothiazolyl(CF 3)carbene (278a) triplet

Excitation energies and oscillator strengths:

Excited State 1: ?Spin -A 2.1447 eV 578.09 nm f=0.0103 54A -> 56A -0.14718 53B -> 54B 0.94866 53B -> 55B -0.29655 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: ?Spin -A 2.3041 eV 538.09 nm f=0.0002 50B -> 55B 0.10903 52B -> 55B 0.13110 53B -> 54B 0.29179 53B -> 55B 0.93802

Excited State 3: ?Spin -A 2.7547 eV 450.08 nm f=0.0020 48B -> 55B -0.14853 52B -> 54B 0.49632 52B -> 55B 0.84755 53B -> 55B -0.13452

Excited State 4: ?Spin -A 2.8315 eV 437.87 nm f=0.0009 51B -> 54B 0.92424 51B -> 55B -0.36430 51B -> 61B -0.10152

Excited State 5: ?Spin -A 2.8927 eV 428.61 nm f=0.0791 55A -> 56A 0.41115 55A -> 57A -0.14272 52B -> 54B 0.77720 52B -> 55B -0.47653 53B -> 56B 0.12932 330

Excited State 6: ?Spin -A 3.2540 eV 381.02 nm f=0.0011 51B -> 54B 0.36967 51B -> 55B 0.92131

Excited State 7: ?Spin -A 3.7672 eV 329.12 nm f=0.0105 50A -> 56A -0.12485 54A -> 56A 0.23182 54A -> 57A 0.38096 55A -> 56A -0.12808 55A -> 59A 0.14097 50B -> 54B 0.75822 50B -> 55B -0.29678 50B -> 56B 0.10143 52B -> 54B 0.10088 53B -> 56B -0.34491 53B -> 57B -0.10921

Excited State 8: ?Spin -A 3.9413 eV 314.57 nm f=0.0371 50A -> 57A -0.13288 52A -> 57A 0.13574 54A -> 56A 0.25249 54A -> 57A 0.35807 55A -> 56A -0.10841 55A -> 57A 0.62931 50B -> 54B -0.38557 50B -> 55B 0.12867 50B -> 56B 0.16481 52B -> 54B 0.16361 52B -> 56B 0.14989 52B -> 57B -0.20270 53B -> 56B -0.39933

Excited State 9: ?Spin -A 4.1254 eV 300.54 nm f=0.0002 50B -> 54B 0.37669 50B -> 55B 0.90991 53B -> 55B -0.11020

**********************************************************************

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Spectrum: B3LYP predicted IR of benzothiazolyl(CF 3)carbene (278a) triplet

Benzothiazolyl(CF 3)ketenimine (279) singlet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.727346 0.465090 0.669919 2 6 0 3.488494 -0.912424 0.653006 3 6 0 2.273143 -1.416063 0.181578 4 6 0 1.282639 -0.542927 -0.278471 5 6 0 1.544899 0.852881 -0.282069 6 6 0 2.756877 1.349216 0.198606 7 16 0 -0.256782 -1.212396 -0.957927 8 6 0 -1.296680 0.161542 -0.525849 9 6 0 -0.559920 1.253114 -0.723171 10 7 0 0.573995 1.715089 -0.903205 11 6 0 -2.492621 0.057059 0.358006 12 9 0 -3.018671 1.280413 0.595965 13 9 0 -2.201302 -0.502077 1.561424 14 9 0 -3.467714 -0.711233 -0.189205 332

15 1 0 4.672709 0.850376 1.038485 16 1 0 4.246002 -1.601273 1.013705 17 1 0 2.091483 -2.486260 0.188760 18 1 0 2.924476 2.421016 0.185324 ------

Zero-point correction= 0.110713 (Hartree/Particle) Sum of electronic and zero-point Energies= -1097.677089

TD B3LYP of benzothiazolyl(CF 3)ketenimine (279) singlet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 2.6761 eV 463.30 nm f=0.0162 54 -> 55 0.63692 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 3.5607 eV 348.20 nm f=0.0120 52 -> 55 -0.10793 53 -> 55 0.66951

Excited State 3: Singlet-A 3.8410 eV 322.79 nm f=0.0332 52 -> 55 0.66370 53 -> 55 0.10619

Excited State 4: Singlet-A 4.3616 eV 284.26 nm f=0.0031 54 -> 56 0.66174 54 -> 57 0.14023

Excited State 5: Singlet-A 4.6993 eV 263.83 nm f=0.0251 53 -> 56 -0.25038 54 -> 56 -0.11387 54 -> 57 0.63615

Excited State 6: Singlet-A 4.9481 eV 250.57 nm f=0.0135 51 -> 55 0.65245 54 -> 58 0.14559

Excited State 7: Singlet-A 5.3740 eV 230.71 nm f=0.0961 50 -> 55 -0.12192 52 -> 56 0.19608 52 -> 57 -0.27249 53 -> 56 0.50938 53 -> 57 0.12061 54 -> 57 0.16687 54 -> 58 -0.18127

Excited State 8: Singlet-A 5.4259 eV 228.51 nm f=0.0334 333

50 -> 55 0.13269 52 -> 56 -0.17135 52 -> 57 -0.16928 53 -> 56 0.18951 54 -> 58 0.57066 54 -> 59 -0.12528

Excited State 9: Singlet-A 5.7245 eV 216.59 nm f=0.0070 50 -> 55 0.41164 52 -> 57 -0.11289 53 -> 57 -0.13874 53 -> 58 0.16727 54 -> 58 -0.17754 54 -> 59 -0.38594 54 -> 62 0.17479

******************************************************

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Spectrum: B3LYP predicted IR of benzothiazolyl(CF 3)ketenimine (279) singlet

Benzothiazolyl(CF 3)ketenimine (279) triplet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------334

1 6 0 4.033825 0.441099 0.035173 2 6 0 3.787433 -0.940923 0.035353 3 6 0 2.481070 -1.419024 0.010808 4 6 0 1.401654 -0.522710 -0.013170 5 6 0 1.643570 0.879258 -0.013304 6 6 0 2.974710 1.337286 0.010965 7 16 0 -0.225243 -1.226696 -0.053218 8 6 0 -1.222428 0.229551 -0.064213 9 6 0 -0.610737 1.462463 -0.046066 10 7 0 0.610984 1.807323 -0.034476 11 6 0 -2.705116 0.034279 0.011480 12 9 0 -3.375014 1.075181 -0.518173 13 9 0 -3.141306 -0.108921 1.294178 14 9 0 -3.092009 -1.090667 -0.646915 15 1 0 5.054346 0.810498 0.053880 16 1 0 4.614236 -1.643777 0.054538 17 1 0 2.292930 -2.488953 0.010045 18 1 0 3.136545 2.410091 0.010397 ------

Zero-point correction= 0.109841 (Hartree/Particle)

Sum of electronic and zero-point Energies= -1097.661734

TD B3LYP of benzothiazolyl(CF 3)ketenimine (279) triplet

Excitation energies and oscillator strengths:

Excited State 1: ?Spin -A 2.6977 eV 459.59 nm f=0.0097 53A -> 57A -0.22638 55A -> 56A -0.35024 55A -> 57A 0.13774 52B -> 54B -0.17979 52B -> 56B 0.16967 53B -> 54B 0.88992 53B -> 57B 0.13030 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: ?Spin -A 2.7558 eV 449.90 nm f=0.0013 55A -> 56A 0.87141 52B -> 54B 0.34289 53B -> 54B 0.40597

Excited State 3: ?Spin -A 3.2216 eV 384.85 nm f=0.0001 54A -> 56A -0.56553 54A -> 62A 0.11540 49B -> 55B 0.17663 335

52B -> 55B -0.37607 53B -> 55B 0.72271

Excited State 4: ?Spin -A 3.3367 eV 371.57 nm f=0.0464 55A -> 56A -0.29884 55A -> 57A -0.39780 51B -> 55B 0.10346 52B -> 54B 0.82089 52B -> 56B 0.12806

Excited State 5: ?Spin -A 3.5108 eV 353.16 nm f=0.0007 54A -> 56A 0.68941 54A -> 62A -0.11903 51B -> 54B 0.37420 52B -> 55B 0.13000 53B -> 55B 0.57825

Excited State 6: ?Spin -A 3.5597 eV 348.30 nm f=0.0024 54A -> 56A -0.21357 55A -> 57A -0.21490 51B -> 54B 0.89580 53B -> 55B -0.27606

Excited State 7: ?Spin -A 3.6100 eV 343.45 nm f=0.0808 55A -> 56A -0.11652 55A -> 57A 0.85129 51B -> 54B 0.19674 52B -> 54B 0.33401 52B -> 57B -0.11401 53B -> 56B -0.22516

Excited State 8: ?Spin -A 3.7824 eV 327.80 nm f=0.0015 54A -> 56A -0.34063 49B -> 55B -0.11412 52B -> 55B 0.90045 53B -> 55B 0.19623

Excited State 9: ?Spin -A 4.0451 eV 306.51 nm f=0.0027 52A -> 56A -0.31664 53A -> 57A -0.62300 55A -> 56A 0.15933 55A -> 62A -0.18031 49B -> 54B -0.10516 50B -> 54B -0.20692 50B -> 57B -0.14540 52B -> 56B 0.34293 53B -> 54B -0.11954 53B -> 56B 0.12970 53B -> 57B 0.62095

**********************************************************************

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B3LYP predicted IR of benzothiazolyl(CF 3)ketenimine (279) triplet

Benzothiazolyl(CF 3)quinoimine (280)

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -4.066215 -1.122445 0.005509 2 6 0 -4.272001 0.304434 0.012453 3 6 0 -3.219310 1.170578 0.008858 4 6 0 -1.850004 0.708233 -0.001885 5 6 0 -1.646576 -0.773686 -0.007977 6 6 0 -2.809459 -1.638211 -0.004722 7 16 0 -0.577219 1.776850 -0.009279 8 6 0 0.715741 -0.878760 -0.015979 9 7 0 -0.484091 -1.380732 -0.015360 10 6 0 1.942216 -0.758458 -0.018576 11 6 0 3.258998 -0.147690 0.001366 12 9 0 3.849711 -0.316705 1.212284 13 9 0 3.238569 1.189659 -0.242357 14 9 0 4.080637 -0.694366 -0.931219 337

15 1 0 -4.928218 -1.782216 0.008814 16 1 0 -5.287495 0.689603 0.020524 17 1 0 -3.376851 2.243576 0.013679 18 1 0 -2.623896 -2.706705 -0.009681 ------

Zero-point correction= 0.109012 (Hartree/Particle) Sum of electronic and zero-point Energies= -1097.643935

TD B3LYP of benzothiazolyl(CF 3)ketenimine (280) quinoimine

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 0.9155 eV 1354.31 nm f=0.0001 54 -> 55 0.64171 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.0654 eV 600.30 nm f=0.0005 52 -> 55 0.67867

Excited State 3: Singlet-A 2.2072 eV 561.72 nm f=0.0589 50 -> 55 -0.13324 51 -> 55 -0.13400 53 -> 55 0.56326

Excited State 4: Singlet-A 3.4736 eV 356.93 nm f=0.1636 51 -> 55 0.61109 53 -> 56 -0.14130 54 -> 58 -0.12956

Excited State 5: Singlet-A 4.0766 eV 304.14 nm f=0.0269 50 -> 55 0.60020 53 -> 56 0.30325

Excited State 6: Singlet-A 4.1588 eV 298.13 nm f=0.0001 49 -> 55 -0.14607 54 -> 56 0.67962

Excited State 7: Singlet-A 4.2953 eV 288.65 nm f=0.0005 49 -> 55 0.66847 54 -> 56 0.15497 54 -> 57 -0.11308

Excited State 8: Singlet-A 4.4545 eV 278.33 nm f=0.0010 49 -> 55 0.12023 54 -> 57 0.68928

Excited State 9: Singlet-A 5.0997 eV 243.12 nm f=0.0535 338

48 -> 55 0.12262 53 -> 57 0.60807 54 -> 58 -0.21894

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Spectrum: B3LYP predicted IR of benzothiazolyl(CF 3)ketenimine (280) quinoimine

Benzoxazolyl(CF 3)diazirine (288a)

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 4.284911 0.355507 0.000398 2 6 0 4.034835 -1.032014 -0.000256 3 6 0 2.734213 -1.545374 -0.000652 4 6 0 1.722468 -0.597246 -0.000355 5 6 0 1.941347 0.787327 0.000287 6 6 0 3.247204 1.287959 0.000682 7 8 0 0.358350 -0.799194 -0.000629 8 6 0 -0.156009 0.468884 -0.000113 9 7 0 0.705180 1.437062 0.000433 10 6 0 -1.618347 0.618596 -0.000281 11 6 0 -2.514059 -0.604479 0.000338 12 9 0 -3.811211 -0.235480 0.000670 339

13 9 0 -2.302541 -1.373341 1.090475 14 9 0 -2.303305 -1.373970 -1.089505 15 7 0 -2.161470 1.858565 0.609572 16 7 0 -2.161445 1.857933 -0.611472 17 1 0 5.313074 0.703747 0.000689 18 1 0 4.873501 -1.721153 -0.000459 19 1 0 2.529845 -2.609977 -0.001154 20 1 0 3.435054 2.356174 0.001190 ------

Zero-point correction= 0.124140 (Hartree/Particle) Sum of electronic and zero-point Energies= -884.209034

TD B3LYP of benzoxazolyl(CF 3)diazirine (288a)

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 3.1695 eV 391.18 nm f=0.0325 54 -> 58 -0.15941 57 -> 58 0.66069 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 3.7948 eV 326.72 nm f=0.0018 56 -> 58 0.70028

Excited State 3: Singlet-A 4.6645 eV 265.80 nm f=0.0136 53 -> 58 -0.12183 54 -> 58 0.64576 57 -> 58 0.18490

Excited State 4: Singlet-A 4.8159 eV 257.45 nm f=0.0000 55 -> 58 0.70215

Excited State 5: Singlet-A 4.8526 eV 255.50 nm f=0.2845 56 -> 59 0.33841 56 -> 60 0.13713 56 -> 61 -0.12369 57 -> 59 0.52857 57 -> 60 -0.18116

Excited State 6: Singlet-A 5.0135 eV 247.30 nm f=0.1090 56 -> 59 0.51479 57 -> 59 -0.35890 57 -> 60 -0.25782

Excited State 7: Singlet-A 5.7708 eV 214.85 nm f=0.1205 56 -> 59 0.23294 56 -> 61 0.31449 340

57 -> 60 0.51890 57 -> 61 0.18620

Excited State 8: Singlet-A 5.8570 eV 211.69 nm f=0.0011 55 -> 59 0.69039

Excited State 9: Singlet-A 6.0897 eV 203.60 nm f=0.0169 53 -> 58 0.50491 54 -> 58 0.10739 56 -> 60 -0.23571 56 -> 61 -0.14715 57 -> 61 0.35484

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Spectrum: B3LYP predicted IR of benzoxazolyl(CF 3)diazirine (288a)

Benzoxazolyl(CF 3)diazirine (288b)

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 4.117272 -0.984716 0.000015 2 6 0 4.290993 0.414394 -0.000007 3 6 0 3.201756 1.291086 -0.000024 4 6 0 1.953259 0.687196 -0.000020 5 6 0 1.751640 -0.700130 0.000009 341

6 6 0 2.849247 -1.566382 0.000025 7 8 0 0.711810 1.285542 -0.000030 8 6 0 -0.158836 0.221631 -0.000009 9 7 0 0.378325 -0.954531 0.000014 10 6 0 -1.587121 0.561206 -0.000010 11 7 0 -2.001666 1.851215 -0.610949 12 7 0 -2.001669 1.851158 0.611048 13 6 0 -2.608432 -0.562747 -0.000026 14 9 0 -3.857798 -0.045753 -0.000171 15 9 0 -2.487918 -1.344711 -1.090371 16 9 0 -2.488114 -1.344526 1.090509 17 1 0 4.995437 -1.622852 0.000024 18 1 0 5.296610 0.823061 -0.000009 19 1 0 3.323793 2.368301 -0.000038 20 1 0 2.710546 -2.642053 0.000042 ------

Zero-point correction= 0.124109 (Hartree/Particle) Sum of electronic and zero-point Energies= -884.208513

TD B3LYP of benzoxazolyl(CF 3)diazirine (288a)

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 3.0496 eV 406.56 nm f=0.0185 54 -> 58 -0.15502 57 -> 58 0.66751 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 3.6688 eV 337.94 nm f=0.0061 56 -> 58 0.69960

Excited State 3: Singlet-A 4.5635 eV 271.69 nm f=0.0114 53 -> 58 -0.13261 54 -> 58 0.64383 57 -> 58 0.17972

Excited State 4: Singlet-A 4.8314 eV 256.62 nm f=0.1749 56 -> 59 0.44812 56 -> 60 0.13227 57 -> 59 0.43909 57 -> 60 -0.23184

Excited State 5: Singlet-A 4.8499 eV 255.64 nm f=0.0000 55 -> 58 0.70183

Excited State 6: Singlet-A 5.0339 eV 246.30 nm f=0.2720 56 -> 59 -0.42192 57 -> 59 0.46500 342

57 -> 60 0.21903

Excited State 7: Singlet-A 5.7831 eV 214.39 nm f=0.0696 56 -> 59 0.23656 56 -> 61 0.31135 57 -> 60 0.53276 57 -> 61 0.14959

Excited State 8: Singlet-A 5.8162 eV 213.17 nm f=0.0008 55 -> 59 0.68997

Excited State 9: Singlet-A 6.0316 eV 205.56 nm f=0.0020 53 -> 58 0.64680 54 -> 58 0.14630 56 -> 60 0.13464 57 -> 61 -0.17361

**********************************************************************

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Spectrum: B3LYP predicted IR of benzoxazolyl(CF 3)diazirine (288a)

Benzoxazolyl(CF 3)carbene (289a) singlet

Standard orientation: ------343

Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.993265 0.241250 0.002206 2 6 0 3.610629 -1.132968 0.005572 3 6 0 2.284590 -1.544799 0.004357 4 6 0 1.337328 -0.517452 -0.001185 5 6 0 1.692939 0.862085 -0.005415 6 6 0 3.054036 1.252108 -0.003298 7 8 0 0.008019 -0.606118 -0.005041 8 6 0 -0.460702 0.748893 -0.010069 9 7 0 0.567338 1.606504 -0.009684 10 6 0 -1.800453 1.113589 -0.012542 11 6 0 -2.783666 -0.016774 -0.002951 12 9 0 -4.063582 0.414334 -0.083858 13 9 0 -2.694531 -0.728957 1.158554 14 9 0 -2.616462 -0.879037 -1.048650 15 1 0 5.050594 0.485256 0.003940 16 1 0 4.392846 -1.886315 0.008933 17 1 0 1.998288 -2.590014 0.006578 18 1 0 3.326141 2.301831 -0.005790 ------

Zero-point correction= 0.112602 (Hartree/Particle) Sum of electronic and zero-point Energies= -774.669145

TD B3LYP of benzoxazolyl(CF 3)carbene (289a) singlet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 0.9988 eV 1241.38 nm f=0.0006 50 -> 51 0.58357 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.9107 eV 425.95 nm f=0.0136 49 -> 51 0.66577

Excited State 3: Singlet-A 3.4469 eV 359.70 nm f=0.0007 47 -> 51 0.68333

Excited State 4: Singlet-A 3.7480 eV 330.80 nm f=0.5601 48 -> 51 0.58962 49 -> 53 -0.10866

Excited State 5: Singlet-A 4.5682 eV 271.41 nm f=0.0013 50 -> 52 0.66711 50 -> 53 0.17491

Excited State 6: Singlet-A 4.9327 eV 251.35 nm f=0.0004 50 -> 52 -0.19740 344

50 -> 53 0.67020

Excited State 7: Singlet-A 5.2957 eV 234.12 nm f=0.0025 44 -> 51 0.61301 45 -> 51 -0.31953

Excited State 8: Singlet-A 5.3282 eV 232.69 nm f=0.0003 44 -> 51 0.31808 45 -> 51 0.61633

Excited State 9: Singlet-A 5.5196 eV 224.62 nm f=0.0487 46 -> 51 0.61783 48 -> 52 0.23146

**********************************************************************

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Spectrum: B3LYP predicted IR of benzoxazolyl(CF 3)carbene (289a) singlet

Benzoxazolyl(CF 3)carbene (289a) triplet

Standard orientation: ------345

Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -4.097326 -0.324992 0.005977 2 6 0 -3.792512 1.055974 0.003296 3 6 0 -2.474548 1.524019 -0.001340 4 6 0 -1.492377 0.545593 -0.003442 5 6 0 -1.766343 -0.840878 -0.001541 6 6 0 -3.098707 -1.291879 0.003601 7 8 0 -0.136425 0.707135 -0.007810 8 6 0 0.360144 -0.600633 -0.008255 9 7 0 -0.586059 -1.539279 -0.004850 10 6 0 1.720085 -0.799410 -0.013865 11 6 0 2.940834 0.019854 0.000844 12 9 0 4.040007 -0.759772 -0.108273 13 9 0 3.065614 0.736813 1.149431 14 9 0 2.972182 0.914131 -1.022527 15 1 0 -5.138527 -0.631558 0.009978 16 1 0 -4.605896 1.774880 0.004837 17 1 0 -2.234861 2.581132 -0.003444 18 1 0 -3.322621 -2.353002 0.005733 ------

Zero-point correction= 0.112412 (Hartree/Particle) Sum of electronic and zero-point Energies= -774.675278

TD B3LYP of benzoxazolyl(CF 3)carbene (289a) triplet

Excitation energies and oscillator strengths:

Excited State 1: ?Spin -A 2.4714 eV 501.68 nm f=0.0108 50A -> 52A 0.17931 51A -> 52A 0.15058 49B -> 50B -0.52588 49B -> 51B 0.83239 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: ?Spin -A 2.5104 eV 493.88 nm f=0.0004 46B -> 50B -0.15807 48B -> 50B 0.71578 48B -> 51B 0.35100 49B -> 50B -0.45832 49B -> 51B -0.37676

Excited State 3: ?Spin -A 2.8044 eV 442.11 nm f=0.0004 48B -> 50B 0.54639 48B -> 51B 0.22669 49B -> 50B 0.70952 346

49B -> 51B 0.37898

Excited State 4: ?Spin -A 2.9068 eV 426.53 nm f=0.1154 51A -> 52A -0.32439 51A -> 53A -0.21627 48B -> 50B -0.38142 48B -> 51B 0.84305

Excited State 5: ?Spin -A 3.2020 eV 387.21 nm f=0.0006 47B -> 50B -0.46610 47B -> 51B 0.87920 47B -> 57B -0.11832

Excited State 6: ?Spin -A 3.6324 eV 341.33 nm f=0.0005 47B -> 50B 0.88089 47B -> 51B 0.46677

Excited State 7: ?Spin -A 4.0762 eV 304.16 nm f=0.0468 49A -> 52A -0.11661 49A -> 53A -0.15150 50A -> 52A 0.57016 50A -> 53A -0.33072 51A -> 52A 0.14149 51A -> 53A 0.41555 51A -> 55A 0.17066 46B -> 50B 0.10084 46B -> 51B -0.19670 48B -> 51B 0.13228 48B -> 53B -0.29554 49B -> 52B 0.53482 49B -> 53B -0.20683

Excited State 8: ?Spin -A 4.3300 eV 286.33 nm f=0.1449 49A -> 52A -0.14203 50A -> 52A -0.10882 51A -> 52A 0.79344 51A -> 53A -0.36558 51A -> 55A 0.15851 46B -> 50B 0.12201 46B -> 51B -0.23012 48B -> 51B 0.10111 48B -> 52B -0.21721 49B -> 53B 0.21608

Excited State 9: ?Spin -A 4.4713 eV 277.29 nm f=0.0933 46A -> 55A 0.12490 50A -> 53A -0.17379 50A -> 55A -0.11725 51A -> 52A 0.35843 51A -> 53A 0.20367 51A -> 55A -0.28888 46B -> 50B -0.38967 46B -> 51B 0.70998 48B -> 51B 0.14145 347

48B -> 53B -0.10310

**********************************************************************

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Spectrum: B3LYP predicted IR of Benzoxazolyl(CF 3)carbene (289a) triplet.

Benzoxazolyl(CF 3)carbene (289b) singlet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.705762 1.091259 0.001680 2 6 0 4.002962 -0.305266 0.000950 3 6 0 3.018671 -1.282991 -0.000680 4 6 0 1.702920 -0.809881 -0.001481 5 6 0 1.379580 0.578520 -0.000526 6 6 0 2.406497 1.554176 0.001055 7 8 0 0.566623 -1.502337 -0.002970 8 6 0 -0.469087 -0.527451 -0.003317 9 7 0 0.037630 0.712560 -0.001993 10 6 0 -1.763730 -1.029719 -0.003556 11 6 0 -2.835903 0.017460 -0.000738 12 9 0 -4.077346 -0.526273 -0.021301 13 9 0 -2.768341 0.831680 -1.091752 14 9 0 -2.784151 0.790141 1.121121 348

15 1 0 4.530705 1.796155 0.002724 16 1 0 5.045074 -0.610442 0.001718 17 1 0 3.247684 -2.342216 -0.001178 18 1 0 2.162650 2.610703 0.001519 ------

Zero-point correction= 0.112664 (Hartree/Particle) Sum of electronic and zero-point Energies= -774.669051

TD B3LYP of Benzoxazolyl(CF 3)carbene (289b) singlet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 0.9822 eV 1262.30 nm f=0.0007 50 -> 51 0.57994 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.9092 eV 426.18 nm f=0.0140 48 -> 51 -0.13134 49 -> 51 0.65302

Excited State 3: Singlet-A 3.4682 eV 357.48 nm f=0.0006 47 -> 51 0.68450

Excited State 4: Singlet-A 3.7438 eV 331.17 nm f=0.5765 48 -> 51 0.57901 49 -> 51 0.11080 49 -> 53 -0.11508

Excited State 5: Singlet-A 4.5676 eV 271.44 nm f=0.0011 50 -> 52 0.67011 50 -> 53 0.16345

Excited State 6: Singlet-A 4.9223 eV 251.88 nm f=0.0005 50 -> 52 -0.18515 50 -> 53 0.67504

Excited State 7: Singlet-A 5.1989 eV 238.48 nm f=0.0013 45 -> 51 0.69413

Excited State 8: Singlet-A 5.3756 eV 230.64 nm f=0.0019 43 -> 51 0.14689 44 -> 51 0.67369

Excited State 9: Singlet-A 5.3848 eV 230.25 nm f=0.0255 43 -> 51 -0.27532 46 -> 51 0.59979 48 -> 52 0.12491

349

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Spectrum: B3LYP predicted IR of Benzoxazolyl(CF 3)carbene (289b) singlet.

Benzoxazolyl(CF 3)carbene (289b) triplet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.882543 0.987607 0.002846 2 6 0 4.100056 -0.409662 0.004819 3 6 0 3.042087 -1.324454 0.002733 4 6 0 1.771495 -0.769842 -0.001290 5 6 0 1.524194 0.621334 -0.002441 6 6 0 2.600921 1.526046 -0.000671 7 8 0 0.566209 -1.411482 -0.004491 8 6 0 -0.367404 -0.378236 -0.007163 9 7 0 0.169622 0.842573 -0.006288 10 6 0 -1.702561 -0.707530 -0.011970 11 6 0 -2.982504 0.019036 0.000574 12 9 0 -4.015768 -0.851674 -0.098724 13 9 0 -3.090383 0.894853 -1.029641 14 9 0 -3.162450 0.728037 1.144065 350

15 1 0 4.741289 1.651436 0.004104 16 1 0 5.119057 -0.783872 0.007984 17 1 0 3.203240 -2.396395 0.004194 18 1 0 2.423839 2.595931 -0.002266 ------

Zero-point correction= 0.112560 (Hartree/Particle) Sum of electronic and zero-point Energies= -774.675423

TD B3LYP of Benzoxazolyl(CF 3)carbene (289b) triplet

Excitation energies and oscillator strengths:

Excited State 1: ?Spin -A 2.4819 eV 499.56 nm f=0.0106 50A -> 52A 0.17986 51A -> 52A 0.15012 48B -> 50B 0.15381 49B -> 50B -0.35691 49B -> 51B 0.90950 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: ?Spin -A 2.5028 eV 495.39 nm f=0.0007 46B -> 50B -0.16709 48B -> 50B 0.74936 48B -> 51B 0.17746 49B -> 50B -0.53268 49B -> 51B -0.33371

Excited State 3: ?Spin -A 2.8091 eV 441.36 nm f=0.0003 48B -> 50B 0.60694 48B -> 51B 0.10439 49B -> 50B 0.76153 49B -> 51B 0.19460

Excited State 4: ?Spin -A 2.9180 eV 424.89 nm f=0.1174 51A -> 52A -0.31790 51A -> 53A -0.21759 48B -> 50B -0.18302 48B -> 51B 0.90823

Excited State 5: ?Spin -A 3.2232 eV 384.66 nm f=0.0006 47B -> 50B -0.24557 47B -> 51B 0.96449 47B -> 57B -0.11554

Excited State 6: ?Spin -A 3.6662 eV 338.18 nm f=0.0009 47B -> 50B 0.96537 47B -> 51B 0.24578

Excited State 7: ?Spin -A 4.0718 eV 304.50 nm f=0.0462 351

49A -> 52A -0.11131 49A -> 53A -0.15487 50A -> 52A 0.57392 50A -> 53A -0.31784 51A -> 52A 0.13671 51A -> 53A 0.42099 51A -> 55A -0.17616 46B -> 51B -0.22699 48B -> 51B 0.13970 48B -> 53B -0.30284 49B -> 52B 0.53808 49B -> 53B -0.18671

Excited State 8: ?Spin -A 4.3293 eV 286.38 nm f=0.1364 49A -> 52A -0.14294 50A -> 52A -0.10620 51A -> 52A 0.79150 51A -> 53A -0.35746 51A -> 55A -0.16846 46B -> 51B -0.27127 48B -> 51B 0.10545 48B -> 52B -0.21960 48B -> 53B 0.10095 49B -> 53B 0.21547

Excited State 9: ?Spin -A 4.4831 eV 276.56 nm f=0.1012 46A -> 55A -0.13272 50A -> 53A -0.18404 50A -> 55A 0.12200 51A -> 52A 0.36965 51A -> 53A 0.18566 51A -> 55A 0.28973 46B -> 50B -0.21162 46B -> 51B 0.78105 48B -> 51B 0.15493 48B -> 53B -0.10744

**********************************************************************

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Spectrum: B3LYP predicted IR of Benzoxazolyl(CF 3)carbene (289b) triplet.

Benzoxazolyl(CF 3)ketenimine (291) singlet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 -3.683360 0.009150 0.501433 2 6 0 -3.251304 -1.281202 0.158010 3 6 0 -1.949476 -1.506345 -0.289584 4 6 0 -1.067548 -0.430940 -0.357551 5 6 0 -1.508690 0.888007 -0.060231 6 6 0 -2.821113 1.094939 0.377962 7 8 0 0.232381 -0.665346 -0.789812 8 6 0 1.095566 0.305904 -0.320949 9 6 0 0.571190 1.544977 -0.329083 10 7 0 -0.631858 1.919414 -0.480977 11 6 0 2.419102 -0.158991 0.177931 12 9 0 3.100251 0.866864 0.725344 13 9 0 3.189562 -0.694461 -0.802736 14 9 0 2.279053 -1.123473 1.122921 15 1 0 -4.703032 0.166100 0.838005 16 1 0 -3.934000 -2.120507 0.245383 17 1 0 -1.597654 -2.499585 -0.546140 18 1 0 -3.147350 2.107495 0.590698 353

------

Zero-point correction= 0.113246 (Hartree/Particle) Sum of electronic and zero-point Energies= -774.677847

TD B3LYP of benzoxazolyl(CF 3)ketenimine (291) singlet

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 2.1126 eV 586.89 nm f=0.0194 50 -> 51 0.58653 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 3.3286 eV 372.48 nm f=0.0050 49 -> 51 0.68577

Excited State 3: Singlet-A 3.5002 eV 354.22 nm f=0.0886 48 -> 51 0.64639 50 -> 52 0.10982

Excited State 4: Singlet-A 4.3274 eV 286.51 nm f=0.0266 50 -> 52 0.67195

Excited State 5: Singlet-A 4.6516 eV 266.54 nm f=0.0116 49 -> 52 -0.17795 50 -> 53 0.67173

Excited State 6: Singlet-A 5.1504 eV 240.73 nm f=0.0280 46 -> 51 -0.15868 47 -> 51 0.61506

Excited State 7: Singlet-A 5.5247 eV 224.42 nm f=0.0564 48 -> 52 -0.17653 48 -> 53 0.43319 49 -> 52 0.48165 49 -> 53 0.12451

Excited State 8: Singlet-A 5.7135 eV 217.00 nm f=0.0195 44 -> 51 0.10412 45 -> 51 -0.15503 46 -> 51 0.45338 48 -> 53 0.14291 50 -> 55 -0.40817 50 -> 57 0.17708

Excited State 9: Singlet-A 5.8328 eV 212.56 nm f=0.0142 48 -> 52 0.12480 50 -> 54 0.60940 50 -> 55 -0.18797 354

50 -> 56 -0.20020

**********************************************************************

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Spectrum: B3LYP predicted IR of benzoxazolyl(CF 3)ketenimine (291) singlet.

Benzoxazolyl(CF 3)ketenimine (291) triplet

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 3.856833 0.062243 0.000175 2 6 0 3.394032 -1.263667 -0.000019 3 6 0 2.027208 -1.538983 -0.000189 4 6 0 1.129371 -0.474276 -0.000109 5 6 0 1.575753 0.872366 0.000030 6 6 0 2.957059 1.122703 0.000178 7 8 0 -0.215394 -0.765108 -0.000246 8 6 0 -1.098412 0.292663 -0.000165 9 6 0 -0.601740 1.573148 -0.000487 10 7 0 0.635629 1.898390 0.000040 355

11 6 0 -2.527320 -0.144003 -0.000177 12 9 0 -3.349655 0.920350 -0.001602 13 9 0 -2.823514 -0.900706 1.088112 14 9 0 -2.823245 -0.903720 -1.085846 15 1 0 4.923736 0.261128 0.000210 16 1 0 4.102846 -2.085451 0.000035 17 1 0 1.647107 -2.554873 -0.000250 18 1 0 3.291078 2.154852 0.000300 ------

Zero-point correction= 0.109841 (Hartree/Particle)

Sum of electronic and zero-point Energies= -1097.661734

TD B3LYP of benzoxazolyl(CF 3)ketenimine (291) triplet

Excitation energies and oscillator strengths:

Excited State 1: ?Spin -A 2.8258 eV 438.76 nm f=0.0022 49A -> 53A -0.21617 51A -> 52A 0.79528 48B -> 50B -0.40764 48B -> 52B 0.17542 49B -> 50B -0.46504 49B -> 53B -0.13630 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: ?Spin -A 2.9843 eV 415.46 nm f=0.0039 49A -> 53A 0.13417 51A -> 52A 0.44631 51A -> 53A 0.13044 48B -> 50B -0.21810 49B -> 50B 0.86162

Excited State 3: ?Spin -A 3.1676 eV 391.41 nm f=0.0002 50A -> 52A 0.24208 46B -> 51B 0.24703 48B -> 51B 0.66591 49B -> 51B 0.69013

Excited State 4: ?Spin -A 3.4532 eV 359.04 nm f=0.0519 49A -> 53A -0.15343 51A -> 52A 0.31653 51A -> 53A 0.45212 356

47B -> 51B 0.20270 48B -> 50B 0.76195 48B -> 52B 0.14541

Excited State 5: ?Spin -A 3.6011 eV 344.30 nm f=0.0000 48B -> 51B -0.70466 49B -> 51B 0.70358

Excited State 6: ?Spin -A 3.6784 eV 337.06 nm f=0.0004 47B -> 50B 0.99366

Excited State 7: ?Spin -A 3.7746 eV 328.47 nm f=0.0939 49A -> 52A 0.10328 51A -> 52A -0.21862 51A -> 53A 0.84651 47B -> 51B -0.15001 48B -> 50B -0.32209 48B -> 53B 0.14510 49B -> 52B -0.22613

Excited State 8: ?Spin -A 4.0632 eV 305.14 nm f=0.0024 50A -> 52A 0.94489 50A -> 57A -0.17111 48B -> 51B -0.21160 49B -> 51B -0.10785

Excited State 9: ?Spin -A 4.0681 eV 304.77 nm f=0.0625 49A -> 52A 0.11320 51A -> 57A -0.19926 46B -> 50B 0.11714 47B -> 51B 0.92533 48B -> 50B -0.17275

******************************************************************** ** 357

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Spectrum: B3LYP predicted IR of benzoxazolyl(CF 3)ketenimine (291) triplet.

Benzoxazolyl(CF 3)quinoimine (290)

Standard orientation: ------Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z ------1 6 0 4.114078 -0.823597 0.000536 2 6 0 4.219427 0.627094 0.001427 3 6 0 3.125120 1.426888 0.000987 4 6 0 1.777634 0.849471 -0.000564 5 6 0 1.686729 -0.670629 -0.001810 6 6 0 2.908333 -1.446630 -0.001012 7 8 0 0.754492 1.527019 -0.001082 8 6 0 -0.649732 -0.768069 -0.004520 9 7 0 0.547441 -1.302705 -0.003677 10 6 0 -1.852917 -0.546040 -0.005750 11 6 0 -3.195497 0.005431 -0.000738 12 9 0 -3.366382 0.927565 -0.980697 13 9 0 -3.473002 0.607809 1.182996 14 9 0 -4.151272 -0.942291 -0.191231 15 1 0 5.028579 -1.408554 0.001096 358

16 1 0 5.212586 1.068011 0.002471 17 1 0 3.192285 2.509791 0.001617 18 1 0 2.815375 -2.527718 -0.001735 ------

Zero-point correction= 0.111237 (Hartree/Particle) Sum of electronic and zero-point Energies= -774.682017

TD B3LYP of benzoxazolyl(CF 3)quinoimine (290)

Excitation energies and oscillator strengths:

Excited State 1: Singlet-A 1.6095 eV 770.35 nm f=0.0001 50 -> 51 0.67430 This state for optimization and/or second-order correction. Copying the excited state density for this state as the 1-particle RhoCI density.

Excited State 2: Singlet-A 2.6556 eV 466.88 nm f=0.0980 47 -> 51 0.19447 49 -> 51 0.58463

Excited State 3: Singlet-A 2.8925 eV 428.64 nm f=0.0002 48 -> 51 0.68092

Excited State 4: Singlet-A 3.7779 eV 328.18 nm f=0.2466 47 -> 51 0.61054 49 -> 51 -0.13136 49 -> 52 -0.14594 50 -> 55 -0.10563

Excited State 5: Singlet-A 4.6189 eV 268.43 nm f=0.0002 45 -> 51 0.68791

Excited State 6: Singlet-A 4.8425 eV 256.04 nm f=0.0002 50 -> 52 0.68688

Excited State 7: Singlet-A 5.1337 eV 241.51 nm f=0.0011 46 -> 51 0.57443 49 -> 52 -0.22466 49 -> 53 0.29099 50 -> 55 0.10750

Excited State 8: Singlet-A 5.3140 eV 233.32 nm f=0.0003 48 -> 53 0.14596 50 -> 53 0.67184

Excited State 9: Singlet-A 5.5193 eV 224.64 nm f=0.0895 46 -> 51 0.19076 47 -> 52 -0.12944 49 -> 52 0.56439 359

49 -> 53 0.17023 50 -> 54 -0.12442 50 -> 55 -0.15196

********************************************************************** 600

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Spectrum: B3LYP predicted IR of benzoxazolyl(CF 3)quinoimine (290).

B3LYP 6-31+ G** (unscaled) Computed Vibrational Frequencies and Intensities

3-BenozthienylCF 3diazirine (223)

Proteo Intensity Deutero Intensity

Frequency(cm -1) Frequency(cm -1)

3258 3.9 3258 3.9 3215 9.3 3215 9.2 360

3208 14.5 3207 14.4 3198 5.3 3198 5.4 3188 0.4 3188 0.4 1747 39.7 2411 3.4 1641 1.4 1747 39.7 1605 1.1 1641 1.5 1563 13.4 1604 0.7 1495 3.4 1547 14.0 1466 19.5 1495 3.5 1387 12.8 1463 22.7 1365 0.9 1380 14.2 1301 93.4 1364 0.9 1285 41.3 1297 71.5 1219 77.0 1278 97.1 1193 39.9 1194 97.8 1180 137.9 1189 60.7 1165 53.1 1166 97.1 1150 192.5 1151 51.5 1145 74.2 1150 226.2 1070 8.9 1088 3.3 1050 44.9 1048 47.5 1046 11.4 1046 8.9 995 0.1 1006 8.9 956 0.7 995 0.1 936 3.7 956 0.4 889 18.7 914 1.0 870 0.6 870 1.5 823 29.0 850 34.5 808 13.9 775 34.1 773 55.2 772 21.5 750 2.4 745 21.1 745 19.0 734 3.7 716 2.8 716 1.6 689 42.2 700 11.1 637 4.6 668 38.1 614 1.3 612 0.7 567 0.03 590 8.6 550 4.2 561 0.2 510 1.06 550 3.7 506 1.05 509 0.9 462 0.28 494 1.3 438 11.3 462 0.3 413 1.6 438 11.3 407 2.7 409 1.0 406 2.9

Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of proteo and deutero diazirine 223 .

361

3-Benozthienyl(CF 3)carbene 224

F=Frequency, I=Intensity

Singlet I Singlet I Triplet I Triplet I

Syn Anti Syn Anti

F(cm -1) F(cm -1) F(cm -1) F(cm -1)

3282 31.2 3268 15.3 3269 6.2 3264 4.0

3218 7.7 3263 1.9 3213 13.6 3230 2.2

3211 9.4 3213 13.7 3205 11.0 3211 13.7

3201 6.9 3202 7.4 3196 2.4 3201 7.4

3192 1.2 3192 0.4 3188 0.2 3191 0.7

1640 0.7 1639 1.7 1639 2.4 1637 3.2

1608 1.6 1608 0.7 1608 0.7 1607 0.1

1510 73.9 1495 36.3 1499 86.4 1507 157.3

1495 11.7 1493 1.9 1490 8.9 1491 8.3

1470 24.7 1473 6.5 1480 41.4 1481 16.7

1370 2.2 1373 135.5 1360 5.4 1365 85.0

1339 19.4 1360 4.9 1348 41.9 1356 2.6

1291 107.7 1300 49.7 1308 151.6 1304 46.6

1269 7.4 1250 73.4 1274 8.7 1268 27.9

1191 72.1 1195 5.9 1193 96.7 1194 28.7

1178 549.4 1176 429.5 1182 283.8 1179 309.2

1158 30.8 1162 5.4 1158 34.0 1161 2.3

1132 26.6 1133 112.2 1139 114.5 1137 141.0

1113 280.9 1110 169.8 1107 177.0 1105 202.7

1058 16.8 1057 284.9 1069 275.3 1062 12.1

1040 5.4 1054 8.0 1062 59.2 1059 290.2 362

1009 4.9 1052 15.9 1046 8.5 1051 15.2

1007 198.8 1003 5.4 996 0.1 997 2.1

969 0.6 963 0.7 958 0.5 958 0.3

927 76.5 917 64 888 13.3 906 1.9

883 0.4 876 0.4 872 0.2 869 0.3

853 12.4 859 11.0 847 51.2 826 57.7

834 44.2 832 33.9 776 4.0 766 48.0

778 11.1 770 57.8 768 52.6 757 0.6

774 49.7 756 3.1 734 7.2 733 4.7

746 16.4 739 6.4 718 4.7 712 3.8

720 1.9 712 3.9 707 33.4 707 38.9

662 0.2 690 4.4 660 3.2 662 0.2

645 26.6 636 26.7 640 26.9 637 33.2

622 4.3 617 1.6 604 0.1 598 0.1

556 6.0 554 3.3 566 0.7 560 0.6

542 1.8 543 9.7 540 3.9 538 0.9

509 0.9 501 3.9 504 0.2 499 1.0

505 5.3 500 2.1 486 0.8 488 0.7

490 1.7 466 0.8 483 0.3 476 0.2

441 1.4 429 6.2 432 5.3 428 3.8

422 6.9 407 2.2 405 1.3 403 0.2

Table . B3LYP G-31+** calculated IR frequencies and their corresponding intensities of singlet and triplet carbenes 224.

Bicyclic intermediate 232

Proteo Intensity Deutero Intensity Frequency(cm -1) Frequency(cm -1)

363

3217 10.8 3217 10.8 3209 10.3 3209 10.3 3201 2.9 3201 2.9 3190 1.4 3189 1.4 3150 13.5 2324 7.9 1868 160.5 1866 161 1634 14.1 1634 14 1599 8.7 1599 8.7 1485 10.2 1485 10.2 1463 21.3 1463 21.2 1348 53.1 1346 41.4 1310 137.4 1304 109.8 1293 25.1 1282 187.6 1254 105.9 1192 15.0 1191 11.6 1176 90.0 1173 123.1 1155 239.7 1154 232.4 1131 121.1 1132 123.6 1126 288.6 1126 317.6 1109 14.5 1116 16.8 1063 8.9 1064 13.8 1045 9.7 1045 10.6 993 0.1 998 10.7 962 76.5 993 0.5 954 0.7 957 24.7 928 13.2 951 13.3 875 0.1 874 0.1 825 4.9 795 6.6 780 19.1 761 74.1 753 62.2 743 2.1 739 3.4 732 3.7 725 2.3 695 4.7 695 4.2 690 26.1 668 13.4 642 32.0 639 33.7 619 3.5 607 3.7 591 24.3 586 23.7 544 0.5 542 0.5 496 2.0 491 1.6 485 3.0 484 3.3 476 1.1 475 1.4 463 2.9 450 3.9 426 4.5 422 2.4 411 4.7 406 5.3

Table . B3LYP G-31+** calculated IR frequencies and their corresponding intensities of proteo and deutero cyclopropene 232 .

3-Benozthienyl(CF 3)ring-opened carbene 233 364

F=Frequency, I=Intensity

Proteo I Proteo I Deutero I Singlet Triplet Singlet F(cm -1) F(cm -1) F(cm -1) 3221 6.7 3237 9.4 3221 6.8 3207 10.4 3216 11.8 3207 10.5 3199 1.7 3207 9.2 3195 7.9 3195 7.9 3194 3.7 3180 1.5 3180 1.6 3184 0.9 2361 0.9 1635 21.2 1612 0.2 1635 21.1 1576 20.4 1585 6.3 1575 18.1 1512 67.9 1512 21.8 1491 91.4 1464 15.6 1465 5.7 1463 28.8 1463 16.8 1456 50.9 1459 11.6 1404 71.6 1388 59.4 1390 92.3 1336 15.1 1318 0.1 1336 15.4 1284 126.5 1304 126.1 1283 77.5 1276 110.0 1278 64.8 1250 113.9 1250 118.7 1262 196.6 1203 148.0 1192 1.1 1187 0.8 1192 10.6 1157 256.4 1159 208.9 1157 260.8 1153 62.2 1145 50.0 1146 12.9 1145 57.4 1136 277.9 1114 165.6 1093 78.8 1130 37.7 1083 5.8 1072 41.0 1068 12.2 1049 2.5 1048 0.5 1048 13.3 1016 0.1 1016 0.1 989 0.0 987 0.8 987 1.2 947 1.0 949 36.5 896 20.3 883 36.5 880 0.2 895 65.9 866 0.1 872 26.9 880 0.1 861 6.9 849 9.6 870 13.2 826 23.2 812 23.9 851 13.1 758 69.8 778 73.4 777 62.1 726 27.3 756 1.6 714 2.3 705 23.9 714 2.8 708 25.2 701 0.2 708 24.1 689 2.8 682 2.0 689 2.9 629 0.8 647 7.8 597 7.6 597 7.4 596 4.8 592 0.0 556 2.6 549 2.3 554 2.4 540 3.1 534 0.3 539 2.8 477 2.2 493 0.1 472 2.7 464 2.8 449 4.7 462 4.6 461 3.1 442 4.1 457 1.4 441 0.4 437 0.2

Table . B3LYP G-31+** calculated IR frequencies and their corresponding intensities of proteo and deutero ring expanded carbene 233 . 365

3-Benozthienyl(CF 3)spiro product 234

Proteo Intensity Deutero Intensity Frequency(cm -1) Frequency(cm -1)

3290 7.2 3212 12.4 3213 12.4 3205 16.3 3205 16.9 3193 8.4 3193 8.5 3184 0.5 1839 145.2 2478 14.9 1642 5.9 1781 145.3 1627 21.7 1642 5.9 1490 3.1 1627 21.3 1477 35.4 1490 3.1 1384 17.1 1477 34.8 1314 39.4 1384 16.2 1293 12.1 1313 36.2 1245 424.7 1292 11.9 1185 7.7 1239 422.2 1163 228.9 1185 7.8 1147 251.9 1162 229 1145 30.1 1146 253 1118 0.4 1144 32.8 1055 17.3 1116 0.5 1030 28.7 1055 18.1 1026 8.7 1026 7.4 988 0.1 989 41.6 947 6.9 988 1.5 937 13.2 944 0.6 872 0.3 873 0.2 820 47.2 817 9.8 790 7.1 796 9.1 780 20.3 777 20.6 748 49.6 748 56.3 736 7.6 718 4.2 717 9.8 716 10.2 678 32.4 702 3.5 629 9.4 674 38.1 578 9.9 614 13.3 564 2.4 563 1.1 513 7.2 545 9.5 484 10.0 507 4.2 465 1.7 483 9.9 443 5.2 453 3.7 430 6.5 431 10.6 401 1.2 422 0.2

366

Table . B3LYP G-31+** calculated IR frequencies and their corresponding intensities of proteo and deutero spiro product 234 .

3-Benozthienyl(CF 3)methylene cyclopropene 235

F=Frequency, I=Intensity

Proteo I Proteo I Deutero I Deutero I F(cm -1) Isomer F(cm -1) Isomer F(cm -1) F(cm -1)

3321 31.9 3284 17.3 3216 9.7 3216 9.3 3216 9.8 3216 9.4 3211 12.3 3209 14.94 3210 12.3 3209 14.9 3186 9.9 3183 15.3 3186 9.9 3183 15.3 3181 4.8 3177 2.7 3181 4.9 3177 2.7 2498 30.5 2470 23.8 1853 505.6 1851 397.3 1810 555.6 1808 444.4 1659 79.3 1660 73.2 1659 74.6 1660 70.5 1598 178.6 1593 199.3 1589 125.9 1584 134 1542 192.3 1542 241.9 1541 189.9 1541 252.9 1478 26.1 1478 20.1 1478 26.6 1478 19.6 1428 42.0 1426 47.1 1428 40.7 1426 48.4 1337 10.2 1339 17.1 1337 9.8 1339 15.5 1258 362.6 1247 107.7 1253 231.6 1245 41.9 1239 208.1 1238 353.6 1236 333.2 1230 427.8 1194 22.9 1196 41.7 1193 29.8 1194 62.9 1185 7.1 1191 264.6 1185 8.1 1191 269 1177 220.4 1184 12.8 1176 222.8 1184 13.9 1160 286.4 1168 136.9 1160 291.4 1164 113.8 1125 14.4 1125 52.3 1121 138.8 1120 113.9 1114 342.7 1115 172.1 1101 243.1 1104 88.4 1088 48.0 1092 61.5 1086 19.3 1076 71.8 1020 29.6 1019 17.8 1019 24.9 1019 17.7 1009 0.3 1009 0.3 1009 0.3 1009 0.3 970 0.1 969 0.0 970 0.1 969 0.01 950 6.7 960 4.6 862 0.9 861 1.1 862 0.3 864 24.8 807 6.0 818 0.8 860 27.1 861 0.2 780 8.2 770 3.2 800 10.1 791 1.4 763 43.4 764 3.5 763 46.9 765 6.1 752 4.2 760 42.6 757 4.1 760 55.5 737 11.8 732 8.5 734 4.8 732 5.6 722 1.4 728 13.3 677 4.2 688 1.1 676 5.1 683 2.9 643 8.9 636 7.3 631 10.7 625 10.4 626 16.2 623 18.2 599 15.8 603 16.7 367

550 1.2 551 1.4 547 1.8 549 1.06 530 1.1 531 1.1 520 1.4 525 2.37 508 9.5 493 2.4 501 5.9 488 5.9 493 6.7 488 6.9 492 7.6 480 1.1 448 1.9 449 0.7 442 1.5 442 0.8 438 6.3 435 10.0 422 9.3 435 10.9

Table . B3LYP G-31+** calculated IR frequencies and their corresponding intensities of proteo and deutero methylene cyclopropene 235 .

2-Deutero 3-benozthienyl(CF 3)carbene 224

F=Frequency, I=Intensity

Singlet I Singlet I Triplet I Triplet I syn anti syn(e) anti

F(cm -1) F(cm -1) F(cm -1) F(cm -1)

3218 7.7 3263 1.9 3213 13.5 3230 2.2

3211 9.1 3213 13.5 3205 11.0 3212 13.7

3201 7.0 3201 7.5 3196 2.4 3201 7.5

3191 1.2 3192 0.4 3188 0.2 3191 0.7

2425 21.9 2416 9.9 2414 5.8 2410 4.2

1640 0.7 1638 1.7 1639 2.4 1637 3.2

1608 1.6 1608 0.7 1608 0.7 1607 0.2

1504 73.3 1494 20.7 1497 82.6 1505 163

1495 10.9 1490 12.9 1490 17.9 1490 9.2

1469 28.6 1473 6.1 1480 43.1 1481 15.6

1369 1.2 1364 77.9 1360 9.0 1357 21.5

1335 13.4 1357 54.7 1340 10.4 1345 38.9

1268 9.9 1295 66.3 1272 21.4 1287 55.8

1230 485.1 1225 274.7 1263 334.4 1249 174 368

1188 13.4 1191 59.5 1189 7.5 1190 10.9

1161 206.6 1165 130.1 1162 176.7 1164 98.3

1135 68.6 1135 155.5 1142 132.3 1141 224.0

1114 276.9 1121 163.2 1111 217.2 1113 198.8

1075 23.5 1070 14.0 1079 54.9 1074 19.2

1040 5.4 1057 281.4 1069 269.6 1059 289.8

1029 114.9 1054 13.4 1046 10.6 1052 17.4

1009 0.1 1003 5.3 996 0.1 997 2.0

999 106.3 1002 39.6 958 0.1 996 8.6

969 0.5 963 0.7 872 0.1 958 0.3

883 0.4 876 0.1 856 43.6 870 0.4

835 57.9 830 19.6 775 18.9 845 35.1

804 51.6 790 40.4 768 53.9 778 17.7

777 32.5 774 38.5 757 3.3 766 49.6

758 3.2 747 0.7 734 10.4 743 5.6

748 29.9 742 18.1 718 4.7 733 8.1

719 1.9 709 2.4 659 2.6 710 2.9

708 13.2 700 14.8 640 28.8 655 0.2

661 0.1 681 5.7 630 10.9 637 33.4

643(29) 28.8 636 26.3 566 0.9 627 13.4

584 0.1 590 0.1 540 7.2 560 0.7

551 6.3 550 4.3 532 3.2 538 6.8

534 1.3 536 10.7 504 0.1 532 0.9

505 5.9 500 3.5 483 0.2 499 0.9

498 0.3 486 1.6 465 0.1 476 0.2

490 1.6 465 0.8 430 5.8 464 0.0

441 1.4 424 5.5 403 1.6 426 4.3 369

417 6.1 406 3.0 400 0.6

Table . B3LYP G-31+** calculated IR frequencies and their corresponding intensities of singlet and triplet deuteron carbenes 224 .

N-Methyl-2-indolyl(CF 3)diazirine (244)

Frequency(cm -1) Intensity 1757 49 1659 6 1582 16 1511 8 1498 43 1493 14 1468 5 1425 49 1400 35 1377 21 1352 18 1298 114 1261 37 1205 77 1194 53 1176 72 1171 192 1154 20 1152 195 1144 38 1119 6 1063 8 960 76 818 23 767 21 750 42 709 29 664 12 370

594 6 535 6

Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of N-methyl-2-indolyl(CF 3)diazirine 244 .

N-Methyl-2-indolyl(CF 3)carbene (245)

F=Frequency, I=Intensity

Singlet I Singlet I Triplet I Triplet I anti syn anti syn F(cm -1) F(cm -1) F(cm -1) F(cm -1) 3289 4 3219 8 3212 16 3213 15 3219 9 3212 16 3205 22 3206 24 3213 14 3197 3 3195 5 3195 6 3199 3 3137 12 3145 4 3126 13 3158 3 3067 33 3102 20 3048 43 3109 18 1669 149 3035 54 1635 68

3043 49 1591 5 1637 61 1567 140

1674 117 1581 83 1561 165 1527 18

1599 119 1554 16 1527 31 1510 10

1589 6 1517 8 1494 10 1505 8

1507 8 1506 13 1486 40 1489 32

1506 25 1496 57 1410 66 1472 14

1495 60 1470 20 1396 18 1415 50

1454 7 1425 39 1350 16 1391 14

1407 48 1408 58 1282 193 1368 9

1394 11 1394 12 1250 66 1333 38

1318 6 1322 84 1183 422 1289 280

1266 175 1277 159 1179 102 1253 21 371

1237 64 1234 48 1169 38 1182 5

1191 17 1194 8 1145 8 1175 483

1185 514 1175 50 1144 43 1169 95

1178 20 1171 227 1113 7 1147 39

1156 163 1151 316 1097 261 1144 15

1108 296 1145 62 1074 305 1097 213

1098 126 1109 180 962 138 1046 292

1022 118 1085 145 824 6 951 131

1016 36 1036 280 776 51 782 46

934 51 906 15 754 46 754 48

893 14 905 13 666 10 737 7

892 11 895 21 583 19 649 9

858 8 804 5 449 7 579 12

819 20 772 16 519 6

774 26 759 46 463 6

756 35 575 16 448 9

755 10 553 12

669 9 539 6

584 19 523 20

583 10 476 10

Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of singlet and triplet carbenes 245 .

N-Methyl-2-indolyl(CF 3) quinoimine 246

372

Anti (e) Intensity Syn Intensity Frequency(cm -1) Frequency(cm -1) 3225 7 3221 7 3207 18 3205 16 3187 13 3192 12 3181 5 3149 2 3120 24 3091 21 3046 29 3078 11 2991 69 3009 29 2307 194 2317 272 1688 22 1645 24 1648 40 1504 20 1570 25 1473 7 1508 8 1457 17 1468 22 1430 9 1427 13 1406 8 1415 6 1381 11 1303 721 1302 659 1256 67 1242 69 1232 22 1128 267 1191 10 1125 299 1169 10 1124 34 1151 24 1105 10 1122 289 1076 292 1116 314 1045 13 1080 291 898 8 881 19 875 29 880 9 834 19 845 24 759 15 779 5 737 30 778 19 635 9 730 16 587 15 639 8 557 9 578 13 460 5 526 12 495 10

Table 10. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of syn and anti quinoimine 246.

373

N-Methyl-2-indolyl(CF 3)ring-opened carbene 236b and 247

Frequency(cm -1) Intensity Frequency(cm -1) Intensity 247 236b

1656 42 1661 34

1648 8 1641 32

1587 23 1599 48

1527 14 1539 10

1507 14 1509 10

1499 8 1498 22

1486 20 1481 18

1474 8 1481 18

1422 60 1410 21

1379 15 1351 72

1367 45 1320 14

1322 65 1312 36

1294 102 1275 102

1288 27 1237 120

1246 45 1195 10

1222 106 1172 28

1194 7 1149 170

1165 52 1147 177

1150 123 1143 94 374

1133 41 1126 36

1108 47 1086 91

1088 254 1018 20

1060 11 979 14

1046 113 954 9

899 12 909 14

867 13 876 18

808 43 782 29

768 51 764 31

756 17 707 9

721 5 673 5

700 41 598 23

677 70 521 10

616 7 511 6

605 13

547 7

Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of zwitterions 236b and 247 .

N-Methyl-3-indolyl(CF 3)diazirine (259)

375

Frequency(cm -1) Intensity

1743 53 1660 10 1587 54 1531 5 1514 7 1504 52 1488 10 1464 13 1428 40 1380 9 1370 28 1304 93 1273 50 1235 101 1188 12 1179 206 1161 37 1156 13 1140 230 1101 35 1075 23 1039 6 1036 38 914 9 879 54 829 8 782 5 754 86 702 32 587 6 570 7

Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of diazirine 259 .

376

N-Methyl-3-indolyl(CF 3)carbene(260)

F=Frequency, I=Intensity

Singlet I Singlet I Triplet I Triplet I Anti Syn anti Syn F(cm -1) F(cm -1) F(cm -1) F(cm -1)

3267 4 3289 14 3271 1 3281 2 3248 2 3219 6 3221 5 3211 14 3212 14 3211 12 3208 15 3204 17 3200 12 3200 11 3199 12 3195 5 3165 4 3190 1 3187 1 3154 6 3127 8 3168 4 3153 6 3098 19 3057 30 3128 7 3098 19 3039 62 1656 2 3058 27 3039 65 1653 6 1631 12 1637 6 1650 7 1623 2

1573 67 1575 24 1620 3 1556 10 1553 86 1559 116 1560 8 1526 33 1511 30 1508 20 1527 32 1509 30 1503 7 1506 12 1510 86 1504 44 1488 13 1487 13 1504 50 1487 10 1482 46 1477 35 1487 10 1475 64 1455 51 1451 51 1480 72 1446 121 1396 2 1394 5 1452 126 1401 1 1380 1 1380 3 1402 5 1364 65

1331 9 1270 97 1364 54 1331 4 1277 92 1244 2 1337 23 1305 197 1239 52 1191 277 1309 75 1260 23 1190 177 1179 300 1253 14 1204 404 1184 291 1144 15 1202 370 1184 2 1156 36 1141 137 1156 40 1155 12 1148 101 1112 296 1154 51 1151 49 1101 130 1102 92 1099 177 1102 247 1095 116 1062 15 1089 139 1082 132 1063 24 1035 9 1056 16 1054 67 1050 283 978 194 1043 17 1049 247 1047 15 911 2 1040 292 1039 10 998 4 846 46 987 3 876 80 914 9 794 33 883 68 800 4 854 13 776 2 783 3 778 3 785 9 765 74 763 5 759 53 775 3 659 13 760 2 734 48 765 70 580 7 759 41 680 2 756 2 560 5 735 49 660 20 719 6 545 2 692 3 581 12 649 6 533 9 653 12 561 3 597 1 498 1 576 9 538 2 571 2 434 10 535 8 485 1 552 5 306 2 471 4 431 5 377

Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of carbene 260 .

Bicyclic intermediate 262

Frequency(cm -1) Intensity

3006 86 1804 213 1650 45 1606 27 1519 21 1504 11 1496 26 1490 41 1462 22 1395 46 1366 13 1332 37 1304 109 1268 165 1247 89 1189 18 1167 79 1148 27 1145 218 1139 52 1118 121 1113 295 1089 43 1044 9 982 9 980 37 972 11 943 10 932 38 822 16 756 55 747 29 677 19 654 24 378

627 11 565 10 562 5 483 7 464 6

Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of bicyclic intermediate 262

Ring extended carbene 264

Singlet Intensity Triplet Intensity Frequency(cm -1) Frequency(cm -1)

3221 12 3226 6 3217 10 3212 16 3202 9 3202 12 3171 4 3158 8 3132 9 3086 25 3062 28 3031 61 1651 18 1622 67 1623 104 1575 24 1574 37 1528 15 1544 39 1491 10 1495 12 1478 13 1476 12 1475 19 1451 8 1465 46 1378 48 1413 13 1369 52 1372 81 1351 93 1352 74 1295 20 1345 72 1261 151 1309 75 1256 26 1273 140 1195 22 1247 90 1171 75 1165 100 1151 260 1149 73 1122 142 1138 190 1090 133 1125 282 1059 6 1102 89 1047 5 1067 13 938 11 1022 33 379

906 42 904 68 870 11 775 36 777 54 747 67 764 18 702 14 704 13 643 6 600 10 528 7 537 11 511 10 517 8 481 7 496 5

Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of singlet and triplet ring extended carbene 264 .

N-Methyl-3-indolyl(CF 3)methylenecyclopropene 265

Frequency(cm -1) Intensity Isomer Intensity Frequency(cm -1)

3281 13 3293 11 3219 9 3214 13 3208 21 3205 19 3176 14 3184 14 3171 13 3080 44 3102 39 3020 52 3019 50 2963 65 2972 126 1860 401 1865 463 1683 55 1682 127 1654 99 1644 50 1617 92 1604 167 1580 90 1567 311 1502 9 1508 6 1430 38 1436 54 1303 26 1339 55 1243 350 1255 73 1232 314 1232 457 1183 40 1192 44 1173 28 1187 8 1169 212 1176 273 1149 280 1160 99 1141 29 1155 63 1094 6 1117 32 1079 5 380

1097 67 1049 26 1012 6 1003 7 955 14 840 11 847 32 837 27 817 7 759 8 766 48 751 42 741 20 739 7 636 7 629 17 628 6 613 6 589 9 586 10 499 8 531 22 464 7

Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of syn and anti methylene cyclopropene 265 .

Benzothiazolyl(CF 3)diazirine (277)

Anti Intensity Syn Intensity Frequency(cm -1) Frequency(cm -1) 1757 68 1740 82 1553 36 1645 9 1470 17 1602 7 1362 22 1580 54 1341 61 1470 12 1302 61 1361 38 1272 45 1339 151 1234 274 1312 33 1187 7 1210 70 1170 88 1188 16 1151 258 1181 272 1081 7 1174 189 1062 113 1103 33 945 34 1069 17 772 54 899 55 738 19 832 20 726 15 772 56 714 12 738 17 540 5 706 25 690 29 548 5

381

Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of syn and anti benzothiazole(CF 3)diazirine 277 .

Benzothiazolyl(CF 3)carbene (278)

F=Frequency, I=Intensity

Singlet I Singlet I Triplet I Triplet I anti syn anti syn F(cm -1) F(cm -1) F(cm -1) F(cm -1) 3227 4 3227 5 3223 6 3222 7 3218 7 3217 6 3214 11 3214 11 3209 4 3209 4 3204 6 3204 5 3196 2 3195 2 3192 1 3193 1 1644 25 1644 44 1625 24 1625 30 1567 18 1567 13 1584 10 1584 7 1515 17 1517 1 1504 47 1519 60 1486 74 1485 94 1471 46 1475 11 1429 47 1437 23 1451 56 1454 24 1377 56 1392 124 1356 13 1357 29 1361 34 1366 66 1314 8 1322 10 1275 3 1276 381 1281 6 1284 58 1243 481 1273 10 1251 318 1269 269 1200 8 1200 1 1187 1 1187 4 1170 237 1167 119 1174 432 1163 377 1150 262 1139 288 1144 63 1142 148 1122 71 1124 275 1122 154 1123 279 1090 297 1084 201 1111 296 1098 291 1059 174 1027 79 1072 21 1071 17 1024 5 1017 146 1035 1 956 1 905 60 981 1 956 1 909 24 823 13 903 22 903 42 836 2 783 46 808 2 846 24 768 63 764 2 784 57 768 66 720 10 739 21 738 18 743 2 710 5 720 5 723 7 720 9 686 5 671 7 697 4 710 5 672 12 612 32 663 4 666 12 594 5 556 2 609 2 619 37 565 1 541 5 580 11 596 1 553 15 501 6 574 10 440 4 501 1 452 8 540 29 413 1 492 4 384 7 509 3 378 3 435 5

Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of syn and anti benzothiazole(CF 3)carbenes 278 .

382

Benzothiazolyl(CF 3)quinoimine (280)

Frequency Intensity (cm -1) 3225 7 3220 4 3206 4 3194 6 2180 98 1607 22 1547 25 1471 67 1424 38 1337 218 1300 297 1228 33 1187 57 1172 35 1119 301 1115 325 1100 77 1091 416 845 8 773 65 769 7 753 10 670 10 628 13 606 4 573 8 565 22 538 3 462 7 455 2

Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of benzothiazole(CF 3) quinoimine.

Benzothiazolyl(CF 3)ketenimine (279)

Singlet Intensity Triplet Intensity Frequency(cm -1) Frequency(cm -1) 3220 7 3220 7 3212 10 3212 8 3202 3 3199 4 1936 263 1659 20 1624 3 1602 25 1477 9 1571 8 383

1468 19 1474 7 1417 170 1466 7 1324 5 1376 150 1291 7 1280 125 1205 214 1265 235 1189 3 1207 55 1174 42 1187 19 1147 288 1153 75 1125 153 1122 144 1121 171 1107 281

1061 3 1076 6

1044 2 962 2

933 90 957 146 878 1 835 7 820 7 771 69 771 67 719 22 727 10 708 2 724 5 686 25 678 10 681 8 618 29 593 2 561 3 546 2 544 8 454 4 511 9 440 2 498 2 402 2 480 8 391 2 434 2 425 1 377 2 Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of singlet and triplet benzothiazolyl(CF 3)ketenimine 279 .

Benzoxazolyl(CF 3)diazirine(288)

Syn Intensity Anti Intensity Frequency(cm -1) Frequency(cm -1)

1759 72 1755 58 1662 10 1663 22 1653 8 1653 13 1606 41 1612 68 1483 27 1483 25 1395 34 1399 45 1352 69 1367 79 1314 11 1271 58 1297 182 1260 70 1270 71 1218 83 1209 71 1185 168 384

1180 146 1181 277 1167 279 1095 9 1092 29 1026 20 1033 89 990 136 1020 18 922 34 926 23 811 8 894 22 770 28 811 11 761 56 772 32 718 22 760 51 584 6 718 21 581 5

Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of syn and anti diazirine 288 .

Benzoxazolyl(CF 3)carbene (289)

F=Frequency, I=Intensity

Singlet I Singlet I Triplet I Triplet I anti syn anti syn F(cm -1) F(cm -1) F(cm -1) F(cm -1)

3232 2 3232 2 3228 4 3228 3 3229 2 3228 3 3224 4 3223 5 3212 4 3211 4 3209 8 3209 8 3199 2 3198 2 3196 2 3195 2 1652 67 1651 85 1640 49 1638 51 1612 68 1612 55 1628 1 1629 5 1554 66 1549 72 1535 49 1537 31 1534 14 1532 22 1511 10 1511 4 1449 14 1451 20 1466 18 1467 21 1400 7 1399 29 1387 12 1388 27 1364 26 1362 73 1318 4 1317 4 1289 80 1332 142 1294 181 1308 208 1246 490 1297 167 1271 33 1276 40 1185 58 1269 179 1243 357 1251 254 1150 135 1184 65 1200 144 1189 195 1141 417 1148 29 1164 59 1159 142 1109 152 1132 368 1132 5 1133 105 1089 303 1111 283 1126 205 1131 117 1010 1 1080 303 1111 299 1100 302 922 28 1011 1 1022 7 1021 3 913 53 977 1 979 188 952 2 874 24 923 4 952 2 951 106 873 3 892 70 910 2 910 3 385

822 17 820 13 895 21 879 29 782 18 793 39 823 8 826 8 768 62 781 35 764 76 765 74 747 3 767 49 745 11 743 11 698 3 733 3 729 1 668 27 665 16 694 3 690 3 626 6 621 14 667 14 668 26 561 6 571 2 620 6 625 6 507 2 561 11 561 10 565 2 451 6 535 2 535 8 561 7 509 14 504 19 509 2 455 1 466 6 448 4 454 7 460 3 447 2

Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of syn and anti carbenes 289 .

Benzoxazolyl(CF 3)ketenimine (291) singlet

Singlet Intensity Triplet Intensity Frequency(cm -1) Frequency(cm -1)

3224 4 3224 5 3220 4 3219 3 3210 5 3210 5 3198 2 3198 2 1741 70 1650 8 1634 7 1609 24 1606 15 1540 7 1492 11 1492 10 1476 42 1473 5 1447 92 1431 90 1343 17 1355 6 1298 1 1308 242 1240 127 1221 11 1208 11 1217 17 1188 19 1180 176 1169 361 1165 38 1166 32 1126 36 1121 209 1115 297 1113 59 1094 290 1108 363 1046 2 962 2 960 3 882 8 887 77 862 6 864 4 821 34 775 16 386

789 34 772 78 766 56 722 25 731 11 600 4 703 26 561 2 643 11 518 2 631 30 475 3 591 3 454 5 562 4 557 12 529 7 504 5

Table 19. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of singlet and triplet ketenimine 291 .

Benzoxazolyl(CF 3)quinoimine (290)

Frequency Intensity (cm -1) 3221 7 3219 3 3203 3 3189 9 2244 98 1726 81 1674 5 1619 4 1575 31 1459 98 1409 20 1336 358 1298 238 1207 40 1176 2 1150 101 1124 310 1117 287 1089 514 887 20 879 2 787 30 774 6 749 52 387

696 15 631 7 609 5 580 8 566 22 539 4 516 4 478 6 417 4 401 1 317 2

Table. B3LYP G-31+** calculated IR frequencies and their corresponding intensities of quinoimine 290 .

Crystal structure data of 3-ketone ( 227 )

Compound 3-(benzothienyl)- trifluoromethylketo ne Formula C10H5OSF3 Formula Weight 230.20 Crystal color and size Colorless plate [mm] 0.31 × 0.27 × 0.09 Crystal system Monoclinic Space group P2 1/c Cell Length a [Å] 10.7385(2) Cell Length b [Å] 12.3622(2) Cell Length c [Å] 7.4071(1) Cell Angle α [o] 90.00 Cell Angle β [o] 107.903 Cell Angle γ [o] 90.00 Cell volume V [Å 3] 935.69(3) Cell Formula units Z 4 absorption coefficient 0.358 [mm -1] Maximum transmission 0.746 Minimum transmission 0.685 388

F(000) 464 R(int) 0.0316 h indices -14 to 13 k indices -16 to 16 l indices -8 to 9 No. of reflections 13027 Goodness-of-fit 1.020 Independent reflections 2267 Refinement parameters 136 Refinement restraints 0 R1 (all reflections) 0.0669 R1 (I > 2 σ(I)) 0.0476 wR 2 (all reflections) 0.1371 wR 2 (I > 2 σ(I)) 0.1228

Table. Crystal structure data of 3-ketone 227

389

Spectrum: 1H NMR spectrum of 1-(benzo[b]thiophen-3-yl)-2, 2, 2-trifluoroethanone

(227 )

390

Spectrum: 13 C NMR spectrum of 1-(benzo[b]thiophen-3-yl)-2, 2, 2-trifluoroethanone (227 )

391

Spectrum: 1H NMR spectrum of 1-(benzo[b]thiophen-3-yl)-2, 2, 2-trifluoroethanone oxime (228 )

392

Spectrum: 13 C NMR spectrum of 1-(benzo[b]thiophen-3-yl)-2, 2, 2-trifluoroethanone oxime (228 )

393

Spectrum: 1H NMR spectrum of 1-(benzo[b]thiophen-3-yl)-2, 2, 2-trifluoroethanone O- tosyl oxime (229 )

394

Spectrum: 13C NMR spectrum of 1-(benzo[b]thiophen-3-yl)-2, 2, 2-trifluoroethanone O- tosyl oxime (229)

395

Spectrum: 1H NMR spectrum of 3-(benzo[b]thiophen-3-yl)-3-(trifluoromethyl)-3-H- diaziridine (230 ) 396

Spectrum: 13C NMR spectrum of 3-(benzo[b]thiophen-3-yl)-3-(trifluoromethyl)-3-H- diaziridine (230 )

397

Spectrum: 1H NMR spectrum of 3-(benzo[b]thiophen-3-yl)-3-(trifluoromethyl)-3-H- diazirine (223 )

398

Spectrum: 13C NMR spectrum of 3-(benzo[b]thiophen-3-yl)-3-(trifluoromethyl)-3-H- diazirine (223 )

399

Spectrum: 1H NMR spectrum of 2-deutero-(benzo[b]thiophene) (225i )

400

Spectrum: 1H NMR spectrum of 3-(benzo[b]thiophen-3-yl)-3-(trifluoromethyl)-3-H- diazirine (223i )

401

Spectrum: 1H NMR spectrum of 2, 2, 2-trifluoro-1-(1-methyl-1H-indol-2-yl)ethanone

(240 )

402

Spectrum: 13C NMR spectrum of 2, 2, 2-trifluoro-1-(1-methyl-1H-indol-2-yl)ethanone

(240 )

403

Spectrum: 1H NMR spectrum of 2, 2, 2-trifluoro-1-(1-methyl-1H-indol-2-yl)ethanone oxime (241 )

404

Spectrum: 13C NMR spectrum of 2, 2, 2-trifluoro-1-(1-methyl-1H-indol-2-yl)ethanone oxime (241 )

405

Spectrum: 1H NMR spectrum of 2, 2, 2-trifluoro-1-(1-methyl-1H-indol-2-yl)ethanone )-

O-mesyl oxime (242 )

406

Spectrum: 1H NMR spectrum of 2, 2, 2-trifluoro-1-(1-methyl-1H-indol-2-yl)ethanone )-

O-tosyl oxime (242 )

407

Spectrum: 1H NMR spectrum of 2, 2, 2-trifluoro-1-(1-methyl-1H-indol-2-yl)ethanone )-

O-tosyl oxime

408

Spectrum: 1H NMR of 1-methyl-2-(3-trifluoromethyl)diaziridin-3-yl)-1-indole (243 )

409

Spectrum: 13C NMR spectrum of 1-methyl-2-(3-trifluoromethyl)diaziridin-3-yl)-1-indole (243 )

410

Spectrum: 1H NMR spectrum of 1-methyl-2-(3-trifluoromethyl)diazirin-3-yl)-1-indole (244 )

411

Spectrum: 1H NMR spectrum of 2, 2, 2-trifluoro-1-(1H-indol-3-yl)ethanone (250 )

412

Spectrum: 13 C NMR spectrum of 2, 2, 2-trifluoro-1-(1H-indol-3-yl)ethanone (250 )

413

Spectrum: 1H NMR spectrum of 2, 2, 2-trifluoro-1-(1-methyl-1H-indol-3-yl)ethanone (254 )

414

Spectrum: 13C NMR spectrum of 2, 2, 2-trifluoro-1-(1-methyl-1H-indol-3-yl)ethanone (254 )

415

Spectrum: 1H NMR spectrum of 2, 2, 2-trifluoro-1-(1-methyl-1H-indol-3-yl)ethanone oxime (255 )

416

Spectrum: 13C NMR spectrum of 2, 2, 2-trifluoro-1-(1-methyl-1H-indol-3-yl)ethanone oxime (255 )

417

Spectrum: 1H NMR spectrum of 2, 2, 2-trifluoro-1-(1-methyl-1H-indol-3-yl)ethanone O- tosyl oxime (256 )

418

Spectrum: 13C NMR spectrum of 2, 2, 2-trifluoro-1-(1-methyl-1H-indol-3-yl)ethanone O- tosyl oxime (256 )

419

Spectrum: 1H NMR spectrum of 2, 2, 2-trifluoro-1-(1-methyl-1H-indol-3-yl)ethanone O- mesyl oxime (257 )

420

Spectrum: 13 C NMR spectrum of 2, 2, 2-trifluoro-1-(1-methyl-1H-indol-3-yl)ethanone O- mesyl oxime (257 )

421

Spectrum: 1H NMR spectrum of 1-methyl-3-(3-trifluoromethyl) diazirdin-3-yl)-1H- indole (259 )

422

Spectrum: 1H NMR spectrum of 1-(benzo[d]thiazol-2-yl)-2, 2, 2-trifluorothanone oxime (274 )

423

Spectrum: 13C NMR spectrum of 1-(benzo[d]thiazol-2-yl)-2, 2, 2-trifluorothanone oxime (274 )

424

Spectrum: 1H NMR spectrum of 1-(benzo[d]thiazol-2-yl)-2, 2, 2-trifluorothanone O-tosyl oxime (275 )

425

Spectrum: 13C NMR spectrum of 1-(benzo[d]thiazol-2-yl)-2, 2, 2-trifluorothanone O- tosyl oxime (275 )

426

Spectrum: 1H NMR spectrum of 2-(3-(trifluoromethyl)diaziridin-3-yl)benzo[d]thiazole (276 )

427

Spectrum: 13C NMR spectrum of 2-(3-(trifluoromethyl)diaziridin-3-yl)benzo[d]thiazole (276 )

428

Spectrum: 1H NMR spectrum of 2-(3-(trifluoromethyl)diazirin-3-yl)benzo[d]thiazole (277 )

429

Spectrum: 13C NMR spectrum of 2-(3-(trifluoromethyl)diazirin-3-yl)benzo[d]thiazole (2 77 )

430

Spectrum: 1H NMR spectrum of 1-(benzo[d]oxazol-2-yl)-2, 2, 2-trifluorothanone oxime (284)

431

Spectrum: 13C NMR spectrum of 1-(benzo[d]oxazol-2-yl)-2, 2, 2-trifluorothanone oxime (284 )

432

Spectrum: 1H NMR spectrum of 1-(benzo[d]oxazol-2-yl)-2, 2, 2-trifluorothanone O-tosyl oxime (285 )

433

Spectrum: 13C NMR spectrum of 1-(benzo[d]oxazol-2-yl)-2, 2, 2-trifluorothanone O- tosyl oxime (285 )

434

Spectrum: 1H NMR spectrum of 2-(3-(trifluoromethyl)diaziridin-3-yl)benzo[d]oxazole (286 )

435

Spectrum: 1H NMR spectrum of 2-(3-(trifluoromethyl)diazirin-3-yl)benzo[d]oxazole (287 )

436

Spectrum: 13C NMR spectrum of 2-(3-(trifluoromethyl)diazirin-3-yl)benzo[d]oxazole (287 )