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PDF (Detailed Experimental Procedures, Full CO Coupling Chemistry of a Terminal Mo Carbide: Sequential Addition of Proton, Hydride, and CO Releases Ethenone Joshua A. Buss, Gwendolyn A. Bailey, Julius Oppenheim, David G. VanderVelde, William A. Goddard III, and Theodor Agapie Division of Chemistry and Chemical Engineering, California Institute of Technology, 1200 E. California Blvd. MC 127-72, Pasadena, CA, USA Supporting Information Contents Experimental Details S3 General Considerations S3 Carbide–CO Coupling from Carbide 1 S3 In situ generation of carbide 1 S3 Figure S1— Partial 13C{1H} (126 MHz, THF, -50 °C) and 31P{1H} (202 MHz, THF, -50 °C) NMR spectra showing clean deprotonation of methylidyne 4 with benzyl potassium. S4 Addition of CO to Carbide 1 to form Metallaketene Complex 2 S4 1 Figure S2— H NMR Spectrum (400 MHz, C6D6, 23 °C) of 2. S5 31 1 Figure S3— P{ H} NMR Spectrum (162 MHz, C6D6, 23 °C) of 2. S5 13 1 Figure S4— C{ H} NMR Spectrum (101 MHz, C6D6, 23 °C) of 2. S6 Figure S5—31P{1H} NMR spectrum (202 MHz, THF, 23 °C) of 2-13C. S6 Figure S6—13C{1H} NMR spectrum (126 MHz, THF, 23 °C) of 2-13C. S6 Preparation of a mixture predominantly of carbide isomer 3 S7 1 13 Figure S7— H NMR Spectrum (400 MHz, C6D6, 23 °C) of 3- C. S8 31 1 13 Figure S8— P{ H} NMR spectrum (162 MHz, C6D6, 23 °C) of 3- C. S8 13 1 13 Figure S9— C{ H} NMR spectrum (101 MHz, C6D6, 23 °C) of 3- C. S8 Sequential Addition of Proton, Hydride, and CO to Carbide 1 S9 Synthesis of Methylidyne 4 S9 1 Figure S10— H NMR Spectrum (300 MHz, C6D6, 23 °C) of 4. S9 13 1 Figure S11— C{ H} NMR Spectrum (101 MHz, C6D6, 23 °C) of 4. S10 31 1 Figure S12— P{ H} NMR Spectrum (121 MHz, C6D6, 23 °C) of 4. S10 1 13 Figure S13— H NMR Spectrum (300 MHz, C6D6, 23 °C) of 4- C. S11 31 1 13 Figure S14— P{ H} NMR Spectrum (121 MHz, C6D6, 23 °C) of 4- C. S11 13 1 13 Figure S15— C{ H} NMR Spectrum (126 MHz, C7D8, -78 °C) of 4- C. S12 Addition of NaBEt3H to 4 – In Situ Formation of 5 and Synthesis of 6 S12 1 13 Figure S16— H NMR Spectrum (500 MHz, C7D8, -80 °C) of 5- C. S13 13 1 13 Figure S17— C{ H} NMR Spectrum (126 MHz, C7D8, -80 °C) of 5- C. S13 31 1 13 Figure S18— P{ H} NMR spectrum (202 MHz, C7D8, -80 °C) of 5- C. S13 Figure S19—Variable temperature 13C{1H} (126 MHz, THF, -50 °C) spectra of methylidene complex 13 13 7- C. Upon warming, clean conversion to 6- C is observed. S15 1 13 Figure S20— H NMR spectrum (600 MHz, C6D6, 23 °C) of 6- C. S16 1 1 13 13 Figure S21—(a) H and (b) H{ C} NMR spectra (600 MHz, C6D6, 23 °C) of 6- C showing resolution 13 of the two PCH2 doublets of triplets into triplets on C decoupling. S16 13 1 13 Figure S22— C{ H} NMR spectrum (101 MHz, C6D6, 23 °C) of 6- C. S17 31 1 13 Figure S23— P{ H} NMR spectrum (126 MHz, C6D6, 23 °C) of 6- C. S17 1 1 13 Figure S24—Partial H/ H COSY NMR spectrum (400 MHz, C6D6, 23 °C) of 6- C. S18 1 13 13 Figure S25—Partial H/ C HSQC NMR spectrum (400/101 MHz, C6D6, 23 °C) of 6- C. S19 1 13 13 Figure S26— Partial H/ C HMBC NMR spectrum (400/101 MHz, C6D6, 23 °C) of 6- C. S19 1 Figure S27— H NMR spectrum (400 MHz, C6D6, 23 °C) of 6. S20 31 1 Figure S28— P{ H} NMR spectrum (126 MHz, C6D6, 23 °C) of 6. S20 CO-Promoted Ethenone Formation from 5-13C S21 S1 1 13 1 31 1 Figure S29— H (500 MHz), C{ H} (126 MHz), and P{ H} (202 MHz) NMR spectra (all C7D8, 13 -78 °C) following the sequential addition of NaBEt3H (A) and CO (B) to 4. S22 13 1 13 Figure S30—Partial C{ H} NMR spectra (101 MHz, C7D8, 23 °C) of EtOAc- C2, 8, without (A) and with (B) selective 13C decoupling. S23 Hydride Addition to Silylcarbyne 9 S23 Addition of NaBEt3H to 9 – In Situ Formation of 10 & 11 S23 1 31 1 Figure S31—Variable temperature partial H (500 MHz, C7D8) and P{ H} (202 MHz, C7D8) NMR spectra monitoring the addition of NaBEt3H to silylalkylidyne 9. S24 13 1 Figure S32. Variable temperature partial C{ H} (126 MHz, C7D8) NMR spectra following the reaction of NaBEt3H with silylalkylidyne 9. S25 1 13 Figure S33—Partial H/ C HSQCAD, HMBC spectra (500/126 MHz, C7D8, -30 °C) of silylcarbene 10. S25 13 13 1 Figure S34—Partial low-temperature C (126 MHz, C7D8) and C{ H} (126 MHz, C7D8) spectra of silylcarbene 10. S26 11 Figure S35— B NMR spectrum (160 MHz, C7D8, -30 °C) following addition of NaBEt3H to 9 at -30 °C. S26 Figure S36—31P{1H} NMR spectra showing the independent synthesis of trimethylsilylketene complex 11 via addition of authentic trimethylsilylketene to N2 adduct 12. S27 Crystallization of Trimethylsilylketene Complex 11 S27 Thermochemical Studies S28 Synthesis of NaBHPh3 S28 1 Figure S37— H NMR spectrum (400 MHz, C6D6, 23 °C) of NaBHPh3. S28 11 Figure S38— B NMR spectrum (128 MHz, C6D6, 23 °C) of NaBHPh3. S28 F Independent Synthesis and Characterization of Methylidyne 4’•X (X = Cl, BAr 4) S29 1 Figure S39— H NMR spectrum (400 MHz, C6D6, 23 °C) of 4’•Cl. S29 13 1 Figure S40— C{ H} NMR spectrum (MHz, C6D6, 23 °C) of 4’•Cl. S30 31 1 Figure S41— P{ H} NMR spectrum (400 MHz, C6D6, 23 °C) of 4’•Cl. S30 1 13 Figure S42—Partial H/ C HMQC spectrum (MHz, C6D6, 23 °C) of 4’•Cl. S30 Protonation of Carbide 1 with [PhAr2PMe]Cl (Ar = 2,4,6-trimethoxyphenyl) S31 31 1 Figure S43— P{ H} NMR spectra (162 MHz, C6D6, 23 °C) showing protonation of carbide 1 with [PhAr2PMe]Cl (Ar = 2,4,6-trimethoxyphenyl). S31 Reaction of Methylidyne 4 with NaBHPh3: variable temperature NMR study S31 31 1 Figure S44—Variable-temperature P{ H} NMR spectra (162 MHz, C6D6) showing low-temperature. conversion of methylidyne 4 to methylidene 5 on addition of NaBHPh3. S32 Computational Details S33 General Considerations S33 Proposed Reaction Mechanism S33 Figure S45—Potential Energy Landscape of C–C Bond Formation S33 Figure S46—Select Molecular Orbitals Near the Minimum Energy Crossing Point S35 Figure S47—Ketene Dihedral Angle as a Function of C–C Distance S36 Additional Considerations S36 Figure S48—trans- and cis-Alkylidene Isomers Considered in DFT Calculations S36 Figure S49—Optimized Structures of the “Endo” and “Exo” SiMe3/CO Isomers of 2 S37 Figure S50—Parent Methylidene and Silylalkylidene Insertions into Mo–P Bonds S37 Cartesian Coordinates of Molecules S38 Crystallographic Information S68 Refinement Details S68 Table S1—Crystal and Refinement Data for Complexes 2, 4, 4’, 6, and 11 S68 Figure S51—Structural Drawing of 2 S69 Figure S52—Structural Drawing of 4 S69 Figure S53—Structural Drawing of 4’ S70 Figure S54—Structural Drawing of 6 S70 Figure S55—Structural Drawing of 11 S71 References S72 S2 EXPERIMENTAL DETAILS General Considerations Note. Below, we distinguish the 13C-labelled compounds from their non-labelled derivatives by adding the modifier “-13C” after the compound number. In the main article, this modifier is omitted for clarity, as mainly the 13C-labelled compounds are discussed. Unless otherwise specified, all operations were carried out in an MBraun drybox under a nitrogen atmosphere or using standard Schlenk and high vacuum line techniques. Solvents for air- and moisture-sensitive reactions 1 were dried over sodium benzophenone ketyl, or by the method of Grubbs. C6D6 was purchased from Cambridge Isotope Laboratories and vacuum transferred from sodium benzophenone ketyl. Solvents, once dried and degassed, were vacuum transferred directly prior to use or stored under inert atmosphere over 4 Å molecular sieves. Molybdenum complexes 92 and 12;3 trimethylsilyl ketene;4 anhydrous tetrabutylammonium 5 6 7 fluoride (TBAF) in MeCN; benzyl potassium; and PhAr2PMeCl (Ar = 2,4,6-trimethoxyphenyl) were prepared and purified according to literature procedures. [Et3NH][Cl] was prepared by condensing HCl gas (freeze-pump-thawed three times and condensed from -78 to -196 °C) onto a frozen pentane solution of dry NEt3. The solids that formed upon warming to room temperature (with stirring) were collected via vacuum filtration and used without further purification. P2Et•HCl was prepared by addition of 1.0 M HCl in anhydrous Et2O (1.1 equiv) to P2Et in THF, followed by concentrating in vacuo to dryness. NaH (purchased as 60% dispersion in mineral oil; Sigma Aldrich) was purified by rinsing with copious pentane and then drying in vacuo. All other chemicals were utilized as received. Trimethylsilyl chloride (dried over CaH2 and distilled prior to use) was purchased from Alfa Aesar. Sodium triethylborohydride (NaBEt3H, 1.0 M in PhMe), triphenylborane, sodium tetraphenylborate, phosphazene base P2Et, anhydrous HCl (1.0 M solution in Et2O), HCl (gas, ≥99%) ,and CO ( ≥99%) were purchased from Sigma Aldrich. NEt3 (dried over CaH2 and distilled prior to use) was purchased from Oakwood Chemicals. 13CO gas was purchased from Monsanto Research; and butane was purchased from Matheson. 1H, 13C{1H}, and 31P{1H} NMR spectra were recorded on Varian 300 MHz, 400 MHz, Varian INOVA-500, or Varian 600 MHz spectrometers with chemical shifts reported in parts per million (ppm).
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