University of North Dakota UND Scholarly Commons Theses and Dissertations Theses, Dissertations, and Senior Projects January 2012 Formal Insertion Reactions Of Stannylenes And Germylenes Into Phosphorus-Halogen Bonds: A Structural And Mechanistic Investigation Joseph Kent West Follow this and additional works at: https://commons.und.edu/theses Recommended Citation West, Joseph Kent, "Formal Insertion Reactions Of Stannylenes And Germylenes Into Phosphorus-Halogen Bonds: A Structural And Mechanistic Investigation" (2012). Theses and Dissertations. 1327. https://commons.und.edu/theses/1327 This Dissertation is brought to you for free and open access by the Theses, Dissertations, and Senior Projects at UND Scholarly Commons. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of UND Scholarly Commons. For more information, please contact [email protected]. FORMAL INSERTION REACTIONS OF STANNYLENES AND GERMYLENES INTO PHOSPHORUS–HALOGEN BONDS: A STRUCTURAL AND MECHANISTIC INVESTIGATION by Joseph Kent West Bachelor of Science, Southwestern Oklahoma State University, 2005 A Dissertation Submitted to the Graduate Faculty of the University of North Dakota in partial fulfillment of the requirements for the degree of Doctor of Philosophy Grand Forks, North Dakota August 2012 PERMISSION Title Formal Insertion Reactions of Stannylenes and Germylenes into Phosphorus–Halogen Bonds: A Structural and Mechanistic Investigation Department Chemistry Degree Doctor of Philosophy In presenting this dissertation in partial fulfillment of the requirements for a graduate degree from the University of North Dakota, I agree that the library of this University shall make it freely available for inspection. I further agree that permission for extensive copying for scholarly purposes may be granted by the professor who supervised my dissertation work or, in his absence, by the chairperson of the department or dean of the Graduate School. It is understood that any copying or publication or other use of this dissertation or part thereof for financial gain shall not be allowed without my written permission. It is also understood that due recognition shall be given to me and to the University of North Dakota in any scholarly use which may be made of any material in my dissertation. ________Joseph West___________________ Signature _______August 3, 2012__________________ Date iii TABLE OF CONTENTS LIST OF FIGURES……………………………………………………………………....vi LIST OF TABLES……………………………………………………………………...viii LIST OF CHARTS…………………………………………………………………….....xi LIST OF SCHEMES…………………………………………………………………….xii LIST OF ABBREVIATIONS………………………………………………………….xvii ACKNOWLEDGEMENTS……………………………………………………………..xix ABSTRACT……………………………………………………………………………...xx CHAPTER I. INTRODUCTION………………………………………………………………1 I.1. Metal-based Reduction of P–Cl Bonds……………………………….2 I.2. Insertion of Group 14 Species into E–X Bonds (E = C, Si, and P; X = Cl, Br, and I)…………………………………………………………….15 Insertions into C–X Bonds……………………………………….15 Insertions into Si–X Bonds………………………………………23 Insertions into P–X Bonds……………………………………….25 I.3. Syntheses and Isolation of Stable Phosphenium Ions……………….31 II. RESULTS AND DISCUSSION……………………………………………...35 II.1. Reactions of Stannylenes and Germylenes with Alkyl- and Arylchlorophosphines……………………………………………………35 Insertion reactions of cyclic stannylenes and germylenes……….35 iv Insertion reactions of acyclic stannylenes and germylenes……...58 Reactions with bis(dichlorophosphino)methane………………....72 Reactions with phosphorus trichloride…………………………...79 II.2. Mechanistic Investigations………………………………………….83 Kinetic studies and comparisons of reactions rates……………...83 P-lone pair “occupation” studies…………………………………86 Reactions of amino(chloro)phosphines…………………………101 Steric effects of non-halide substituents on phosphorus………..116 II.3. Mechanistic Hypotheses…………………………………………...121 Proposed insertion mechanisms………………………………...121 Mechanistic hypotheses for the decomposition of insertion products…………………………………………………………132 II.4. Conclusions………………………………………………………..138 III. EXPERIMENTAL………………………………………………………….140 III.1. Starting Materials and General Procedures……………………….140 III.2. Syntheses………………………………………………………….141 III.3. X-ray Crystallography……………………………………………155 REFERENCES……..…………………………………………………………………..156 v LIST OF FIGURES Figure Page 1. Crystal structure of 186 showing the two independent molecules in the unit cell....27 2. Crystal structure of 4………………………………………………………………..36 3. 31P{1H} NMR spectrum of stannylene insertion product 5………………………...39 4. 31P{1H} NMR spectrum of cyclic oligophosphines 6–10 obtained from the breakdown of 5……………………………………………………………………..40 5. Crystal structure of 15……………………………………………………………...41 6. Crystal structure of 17……………………………………………………………...44 7. Crystal structure of 18……………………………………………………………...48 8. 31P{1H} NMR spectrum of 17 and its monoinsertion intermediate………………..51 9. Crystal structure of 20……………………………………………………………...52 10. Crystal structure of 21……………………………………………………………...54 11. Crystal structure of 26……………………………………………………………...60 12. Crystal structure of 27……………………………………………………………...64 13. Crystal structure of 29……………………………………………………………...69 14. 31P{1H} NMR spectrum of tri-tert-butylcyclotriphosphine 31…………………….71 15. 31P{1H} NMR spectrum for reaction mixture of stannylene 23 with chlorophosphine 19 displaying three separate, yet similar, products………………72 16. Crystal structure of 33………………………………………………………….......74 17. 31P{1H} NMR spectrum of reaction mixture from Scheme 51…………………….77 18. Crystal structure of 44……………………………………………………………...81 vi 19. Kinetics data for addition of carbenoids 2, 22, and 23 to tBu(Ph)PCl 45………….86 20. Crystal structure of 49……………………………………………………………...87 21. Crystal structure of 50……………………………………………………………...90 22. Crystal structure of 53……………………………………………………………...94 23. Crystal structure of 54……………………………………………………………...97 24. Crystal structure of 60…………………………………………………………….102 25. Crystal structure of 62…………………………………………………………….106 26. Crystal structure of 65…………………………………………………………….110 27. Crystal structure of 66…………………………………………………………….113 28. 31P{1H} NMR spectrum of the reaction mixture containing cyclic stannylene 2 and dichlorophenylphosphine 3 (see Scheme 43 for reaction)..………………………118 vii LIST OF TABLES Table Page 1. Isolated diphosphene-bridged compounds and yields from Scheme 6……………...7 2. Isolated phosphinidene-bridged compounds and yields from Scheme 6……………8 3. Yields of diphenylphosphine 47 obtained from the metal reduction of chlorodiphenylphosphine 46 with reaction conditions………………………………..10 4. Isolated phosphanediide salts from Scheme 12……………………………………13 5. Kinetic data for reaction of stannylene 79 with organic halides 74, and 80–93…...17 6. Crystal data for compound 4……………………………………………………….37 7. Selected bond lengths and angles for compound 4………………………………...38 8. Crystal data for compound 15……………………………………………………...42 9. Selected bond lengths and angles for compound 15……………………………….43 10. Crystal data for compound 17……………………………………………………...46 11. Selected bond lengths and angles for compound 17……………………………….47 12. Crystal data for compound 18……………………………………………………...49 13. Selected bond lengths and angles for one of two independent molecules in the unit cell of compound 18…………………………………………………………….50 14. Crystal data for compound 20……………………………………………………...53 15. Selected bond lengths and angles for compound 20……………………………….54 16. Crystal data for compound 21……………………………………………………...56 17. Selected bond lengths and angles for compound 21……………………………….57 18. Crystal data for compound 26……………………………………………………...62 viii 19. Selected bond lengths and angles for compound 26……………………………….63 20. Crystal data for compound 27……………………………………………………...66 21. Selected bond lengths and angles for compound 27……………………………….67 22. Crystal data for compound 29……………………………………………………...70 23. Selected bond lengths and angles for compound 29……………………………….71 24. Crystal data for compound 33……………………………………………………...75 25. Selected bond lengths and angles for compound 33……………………………….76 26. Crystal data for compound 44……………………………………………………...82 27. Selected bond lengths and angles for compound 44……………………………….83 28. Approximate completion times for insertion reactions…………………………….85 29. Crystal data for compound 49……………………………………………………...88 30. Selected bond lengths and angles for compound 49……………………………….89 31. Comparison of Pd–P and Pd–Cl bond lengths for various trans bis(phosphine)palladium dichloride complexes…………………………………89 32. Crystal data for compound 50……………………………………………………...91 33. Selected bond lengths and angles for compound 50……………………………….92 34. Crystal data for compound 53……………………………………………………...95 35. Selected bond lengths and angles for compound 53……………………………….96 36. Crystal data for compound 54……………………………………………………...98 37. Selected bond lengths and angles for compound 54……………………………….99 38. Crystal data for compound 60…………………………………………………….103 39. Selected bond lengths and angles for compound 60……………………………...104 40. Crystal data for compound 62…………………………………………………….107 41. Selected bond lengths and angles for compound 62……………………………...108 ix 42. Crystal data for compound 65…………………………………………………….111 43. Selected bond lengths and angles for compound 65……………………………...112 44. Crystal data for compound 66…………………………………………………….114 45. Selected bond lengths and angles for compound 65……………………………...115 46. Summary of relative completion times of stannylene 2 with monochlorophosphines…………………………………………………………...123 x LIST OF CHARTS Chart Page 1. Proposed