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Fluorosulfanylimination Including Related

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Fluorosulfanylimination Including Related FLUOROSULFANYLIMINATIONINCLUDING RELATED REACTIONS ANDSTRUCTURAL PROBLEMS AND THIAZYLTRIFLUORIDE COI1PLEXES OF THETRANSrrION METALS by Abraham Shanzer Dissertation Subnitted to the Graduate Faculty of the Virginia Polytechnic Institute and State University in partial fulfillment of the requirements for the dec7ee of DOCTOROF PHILOSOPHY in Chemistry APPROVED, Dr. A. F. Clifford, otfo.1/.rman:-- Dr. R. E. Dessy Dr. M. Hudlicky Dr. H. H. McNair Dr. T. c. Ward December, 1976 Blacksburg, Virginia ACKNOWLEDGENENTS I wish to express my sincere gratitude and thanks to Dr. Alan F. Clifford for the opportunity of working on very stimulating problems and for his invaluable guidance, advice and encouragement throughout the course of this study. His perceptive sugeestions and constructive criticisms are greatly appreciated. To Dr. J. C. Schug and my colleague Dana Brewer, I am deeply indebted for their immense patience in performing the molecular orbital calculations and the physical interpretation of the results. Deep appreciation is extended to Dr. R. E. Dessy, Dr. M. Hudlicky, Dr. H. M. McNair and Dr. G. Sanzone for their constant guidance and interest. I am most grateful for the many hours they so kindly spent in stimulating and constructive discussions. I would like to thank most sincerely Victoria Kok, who has given invaluable help with proofreading the thesis in all its stages of preparation. Ny profound gratitude is to my parents, Jacob and Hella Shanzer and to a very special friend, for their continuous encouragement and for providing the motivation to seek a little higher. To them I dedicate this thesis much much love. ii TABLEOF CONTENTS Page ii ACKNOWLI!.'DG}1ENTS• • • • • • • • • • • • • • • • • • • • • • • • LIST OF TABLES • • • • • • • • • • • • • • • • • • • , • • • • vii LIST OF FIGURES • • • • • • • • • • • • • • • • • • • • • • viii INTRODUCTION • • • • • • • • • • • • • • • • • • • • • • • • • 1 Unique Properties of Pentafluorosulfanyl Group • • • • • • • 6 Classification of SFc;-Nitrogen Compounds •••••••••• 8 a. S~ c;NRR• Comp6unds • • • • • • • • • • • • • • • • • • 9 b. S~~NHg C:ompounds • • • • • • • • • • • • • • • • • • 9 c. S~N~ X <!ompounds • • • • • • • • • • • • • • • • • • 9 Synthesis of Pentafluorosulfanyl-Ni trogen SF\N= Compounds • • 10 a. Addition of SF 5c1 to the Ni trllc Grotlp • • • • • • • 10 b, Polar Addition to Thlazyl Trifluoride •••••••• 10 PART I. FLUOROSUU'ANYLIMINATIONINCLUDilW RELATEDREACTIONS ANDSTRUCTURAL PROBLEMS ••••••••••••• . 14 CHAPTERI. PREP,\liATIONOF ANDREACTIONS WITH PENTAFUJOHO- SULFANYLISOCYANATE,s~5 NCO. • • • • • • • • • • • • • 17 A. Nucleophilic Substitution Reactions ••••••••••• 20 1. Nucleophilic Addi ti on • • • • • • • • • • • • • • • • 20 2. Nucleophilic Displacement •••••••••••••• 21 a. Reaction of SF,NCO and (CH3)2SO ••••••••• 22 b. Reaction of SF 5N=O=Owith 'Derizaldehyde ••••• 24 J. Transition Metal Nitrogen Multiple Bond ••••••• 27 B. Exchange Hcactions • • • • • • • • • • • • • • • • • • • 28 1. Reaction of SF SNCO with PClS • , • • • • • • • • , • 28 c. Coupling r~cactions • • • • • • • • • • • • • • • • • • • Jl 1. Fluorination of SF5Ncowith AgF2 • • • • • • • • • • 32 CHAPTER2. PREPARATIONOF AND REACTIONWITH }1ENTAFLUORO- SULFANYLHUNO-SULFUHDIFLUORIDE ••••••••• • • )6 A. Introduction • • • • • • • • • • • • • • • • • • • • • • J6 D, New Method for the Preparation of SF i;N=SF2 a I • I • a e 37 1, Photolysis of Thiazyl Trifluorid~ ••• I • • e e I • J7 iii Page c. F.xchangc Jer ..ctions of SF 5N=S?2 • • • • • • • • • • • • • • 39 1. Reaction Between SF5N~SF2 and PClr. •••• • • • • • • 39 2. Reaction Between SF N=S!•'2 and SiC!4 • • • • • • • • • 42 J. Reaction Between S~N=SF2 and AlClJ •••••• • •• 42 D. Rr,actions With SF N=SCl •••••••••• , •• • , • • 4J 1. Reaction of S~ 5N=SCt 2 with SF5 NH2 • • • • • • • • • • 4J CHAPTERJ. ATIEiff'I'S TO PREFAfl1'! BI3-(PENTAfLUOBOSULfANYL)- CARB0DIIll1IDE,Sl\N=C-=SF 5 • • , , • • • • • • • • • • • 45 • ". Introduction •• • e e e I • • • • • • • • • • • • • • . 45 B. Preparation and Properties of S1'\t;:.PXJ DeJ:iva.tives •••• 47 1, Reaction Between SF5NH2 and 1c15 ...••.. • • • • 46 c. Preparation of Bis-(pcntafluorosulfanyl)- caroocllimide • • • . • • . • • • . • . • • • . • . • • • 51 1. Atternpt!}d !{eactlon Between SF\/i=-PCJ.3 and Sfr.:NCO ••• 51 2, AtteJ11pted Reaction Betwe1:m (Si\NH) 2co and f1c15 • . • . .51 J. Reaction of SF .5H;CC12 With nF'.5NH2 ~. • • • • • • • • • 5?. D. Summa.ry • • • • • , • • • , • • • • • • • • , • • • • • • 53 CHAl='TER4. THE {rJESTION OF ROTATION ABOUT THT~pn-prr BOND IN TIN=Sl'2 COMPOUNDS••••••••• , •••••• , , 55 A. Introduction ti • • e I • • • • • • • • • I I e • • • • • • 55 B. }:olccular Or:bi tal Calculations of Imlnosulfur Dlfluorldcs • • • • • • • • • • • • • • • • • • • • . 57 c. Results and Discussion. • • • • • • • • • • • • ti • • • • .58 D. Nuclear })agnetic Resonance Studies • • • • • • • • • • • • 64 1. Low Ter.1pcra.turo nmr Studies of Pcnta.fluoro:;ulfanyl- imino sulfur dlfluoride • • • • • • • • • • • • • • , 65 2. Low Temperature nrnr Studles of 1''luoroformy r.iminosulfur Dlfluorldc • • • • • • • • • • • • • .• • • • • • • • • 70 E. Summary . 7) EXPERIMENTAL. • • • • • • • • • • • • • • . • • 75 A, Equipment • • • • • • • • • • • • • • . • • • • • • 7.5 1. Vacuum System . • • • . • • • • • . • • • • • • • • • • 76 2. Infrared Spectra • • • • . • . • . • • • • • 76 . J. Nuclear Magnetic . • Resonance Spectra • • • • • • • 77 4. Elemental . • Analysis • • • • • • • • • • • • • • • • • • 77 iv Page B. Starting Materials • • • , • • • •• • • • • • • • • • • • 77 c. Experiments • • . • • • . • . • . • • • , • " • • • 79 1. Preparation of Pentafluorosulfanyl Isocyanate, SF NCO • • • • • • • • , • • , , • • • • • • • • • • • 79 a.5 N,Ni-Bls(pentafluorosulfanyl)urea with COC12 ••• 79 b. N,N'-Bis(pentafluorosulfanyl)urca with C0?2 ••• 60 2. Nuclcor,hll le Su bst.1 tution Reaction • • • • • • • • • • 81 81 a. i1eactlon of SF'~CO with (cH 3) 2so ••• • • • • • • b. Reaction of SF'-.:NCOwith C,;H ci-:o ••••••••• 82 c. Attempted Hieachon Between ~F i::,!ICOwith Oso4 ••• 83 d. ,\ttcmpted Heaction Between sr;Ncowith Cl 3 • • • • 83 c. Attempted Heaction Between Cl~JJ2NCO wl th c1 3 ••• 83 J. 2xchange Reaction •••••••••••• • ••• • • 84 ~· Beact~on of s?5NCO and PCl 5 • • • , • • , • • • • 84 4. Coupl lng •.cactlon • • • • • , • , • , • • • , • , , • 8.5 a. Fluorlnation of SF c,NCO with Ag?? • • • • • • • • • 85 5. New Method for the Preparation of SF '1N=SI~,2 • • • • • • 86 a. Photolysis of Thiazyl Trifluorid~ • • • • • • • • 86 6. Exch~nge Rcaction~.,of ~3~5N=SF';, • r• • • • • • • • • • • • 87 a. hcactions of S.·_ 11N°=Sr2 wi tfi P"l 5 • • • • • • , • • 87 b. Reaction of SF'sN=Sli'2 with S1C14 • • • • • • • , • 89 c. Heaction of s:,'r:;N=SF'2 and AlC1 3 •••••• , ••• 89 7. Reactions wl th SF ,}~"'SCl • • • • • • • • • • • , • • • 91 a. Reactions of dF N~Sg~2 with AgF0 ••• , •••• , 91 b. Reactions of S1"~N=SC12 with SF 5tm2 • • • • • • • • PART II. THIAZYLTRIFLUORIDE COMPLEXES OF THE TRANSITION i~ALS • • • • • • • . • • • • • • • • , • • • • • . 96 A, Introduction . • • • • . 96 B. Result and Discussion • • • • • • . 97 C. Experimental •••• , • • • • • • • • • , • , • • • • 99 1. Hcactlon of Nctal Cartonyl and Thlazyl Trifluoride • • 99 a. Reaction Between Nickel Tetracarbonyl and Thiazyl Trifluoride • • • • • • • • • • • • • • • 99 b. Reaction Between Molybdenum Hexacarbonyl and Thiazyl Trifluoride • • • • • • • • • • • • • • • 100 c. ikactlon Dctwc,~n Iron Pentacarl::onyl and Thiazyl Trifluoride • • • • • • • • • • • • • • • 101 2. Rcactlon of n-Gomplcxcs with Thlazyl Trifluoride • , • 106 a. Reaction Between Fcrrocene and Thiazyl Trifluoride. • • • • • • • • , • , • • • • . , • • 106 D. Summary • • • • • • • • • • • • • • • • • • • • • • . 112 V Page FiEFERENCES. • . llJ VITA • • • • . .. 118 ABSTRACT vi LIST OF TABLES Table Page 1. Types of Compounds with Sulfur(IV) •• . J 2. Types of Comp~unds with Sulfur(VI) • • . 4 J. Substituent Effect on the Barrier to Free Rotation. • • 6J 4. Mass Spectra of the Fraction Collected at -42° • • • • • 90 5, Mass Spectrum of Molybdenum Carbonyl-Thiazyl Trifluoride Complex • • , , , • • , • • • • , • • • • 102 vii LIST OF FIGUR:BS Figure Page 1, Pentafluorosulfanyl-nitrogen, SF~-N, compounds derived from pentafluorosulfanylazomethine • , , , •• , , 12 2. Pentafluorosulfanyl-nitrogen, SF5N, compounds derived from thiazyl trifluoride, ••• , • , , • , , , • 13 J, Fluorine-19 and Hydrogen-1 nmr spectra of Sl4'5N=C(CHJ) 2 , , • • , , , • • , , , , , • , , , • , • • , 2J 4. Fluorine-19 nmr spectrum of SF5N=CHC6H5 • • , • • • • • • 26 5, Fluorine-19 nmr spectrum of SF5N=CC12 ••• , , • , , , • JO 6. 'femperatu:re effects on the fluorination of SF5 NcOwith AgF2 , , • , , , , • • , , , , • , • • • • • • JJ 7, Infrared spectrum of SF5N=SC12 •• , • , • , , • , , • , , 40 8, Fluorine-19 nmr spectrum of SF5N=SC12 , • , , • , • • • • 41 Reaction sequences for the attempted preparation of N,N'-bis(pentafluorosulfanyl)ba.rbiturate , • • • . 46 10, Infrared spectrum of SF5N=PC1J . 49 11. Fluorine nmr spectrum of SF5N=PC1J •••• , ••• , • • • 50 12, Total energy of SF2=N-C N as, a function of rotation about the S=N bond • , •• , ••••••• , • , • , • , 59 lJ. Bond order in SF2=N-C N , , •• , , • , , ••• , , , , , 60 14, Bond order in SF2 =N-F • , , • • • • , , , • , , , , • , • 62 15, Fluorino-19 nmr spectra of SF5N=SF2 at different temperatures , • , , • • • • , , • , • I I I I I I I I I I 67 16. Fluorine-19 nmr spectra of a mixture of SF N=SF and SF5NcO, • ,
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