Silicon, Germanium and Tin Arsines

University of Windsor Scholarship at UWindsor Electronic Theses and Dissertations Theses, Dissertations, and Major Papers 1-1-1971 Silicon, germanium and tin arsines. John W. Anderson University of Windsor Follow this and additional works at: https://scholar.uwindsor.ca/etd Recommended Citation Anderson, John W., "Silicon, germanium and tin arsines." (1971). Electronic Theses and Dissertations. 6092. https://scholar.uwindsor.ca/etd/6092 This online database contains the full-text of PhD dissertations and Masters’ theses of University of Windsor students from 1954 forward. These documents are made available for personal study and research purposes only, in accordance with the Canadian Copyright Act and the Creative Commons license—CC BY-NC-ND (Attribution, Non-Commercial, No Derivative Works). Under this license, works must always be attributed to the copyright holder (original author), cannot be used for any commercial purposes, and may not be altered. Any other use would require the permission of the copyright holder. Students may inquire about withdrawing their dissertation and/or thesis from this database. For additional inquiries, please contact the repository administrator via email ([email protected]) or by telephone at 519-253-3000ext. 3208. SILICON, GERMANIUM AND TIN ARSINES BY John W. Anderson A Dissertation Submitted to the Faculty of Graduate Studies through the Department of Chemistry in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy at the University of Windsor Windsor, Ontario 1971 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. UMI Number: DC52672 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. UMI ® UMI Microform DC52672 Copyright 2009 by ProQuest LLC. All rights reserved. This microform edition is protected against unauthorized copying under Title 17, United States Code. ProQuest LLC 789 E. Eisenhower Parkway PO Box 1346 Ann Arbor, Ml 48106-1346 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. This dissertation has been examined and approved by: 367719 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ABSTRACT A number of silicon, germanium and tin arsines have been prepared by various methods. Primary arsines such as R^MAst^, Si2HÂsH2, MeMl^st^Me^SnAst^ and R 2Si(AsH2)2 (M = Si, Ge; R = H, Me) were prepared from LiAlCAs^)^ and the appropriate halide. Similarly R^MAsMe2 or (R^M)2AsMe were prepared from LiAl(AsHMe)or LiAl(AsMe2)^H. The reaction of excess trisilylarsine with LiAlH^ gave a disilylarsinoaluminate which was used to prepare ( S i H ^ ^ s R (R = H, Me, Me3Si). The tertiary arsines R^MAsR^ and (R3M)2AsR' were prepared from LiAsRj) and LiAsHR' (m= Si, Ge; R = H, Me; R' = Me, Ph). The reaction of (Me^MÂs with a lithium alkyl gave LiAslMMe^^ which was used to prepare (Me3M)2AsR (M = Ge, Sn; R = H, Me and M = S i ; R = H, M e , SiH^). (Me^MjÂs was prepared from Me^MCl and AsH^ in the presence of triethylamine (M = G e , Sn). The reaction of an arsine with a germanium or tin amine was used to prepare (Me^GeÂsR^ ^ and (Me3Sn)2As^ = Me> n = 1-3) • The exchange reaction between a silyl arsine and a germanium or tin halide was used to prepare (R^MÂsR' g_n, Me2Ge(AsMe2) 2> MeGe(AsMe2)3 and Me2Ge(AsH2)2 (R' — Me, Ph; n = 1-3; M = Gej'R = Me, H and M = Sn; R = Me). Primary arsines are best prepared from LiAllAsH^)^ and secondary arsines by acidification of lithium disilylarsinoaluminates or disilyl- arsenides. Tertiary arsines are best prepared from lithium arsenides 11 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. or by exchange reactions (for germanium and tin). Chlorine cleaved the M-As bond to give the two chlorides (M = Si, Ge, Sn) and Chloroboranes cleaved the M-As bond to give the group IV chloride and arsinoboranes. The reaction of AsCl^ with (MH^gAs gave the cyclic arsines (MHÂsJs Germanium and tin amines reacted with group IV arsines to give the mixed arsines Me^GelMe^SnjAsR (R^Me^Ge, Me, Ph), (Me^Si)^sMMe^ (M=Ge, Sn) and Me2M\As(GeMe2)-j]2 (M = Ge, Sn). The vibrational spectra of trimethyliodogermane and trimethylfluorogermane were assigned. iii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS The investigations described in this work were carried out in the chemical laboratories of the University of Southampton, England and the University of Windsor, Ontario, Canada between 1968 and 1971 under the supervision of Dr. J.E. Drake. The author would like to express his gratitude to his supervisor for his unfailing help, encouragement and boundless enthusiasm, to his parents and wife for their encouragement and to Drs. C. Riddle and J. Davis and Messrs. G. Barker and R. Hemmings for valuable discussions and gifts of chemicals. The author would also like to acknowledge the Science Research Council for the award of a maintenance grant, the University of Windsor library for its persistent efforts to hinder this investigation and members of the technical staff for valuable assistance. iv Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. To the many dedicated chemists across the world pushing forward the frontiers of science v Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. Table of Contents Introduction.................................... 1 Chapter 1, Techniques and Starting Materials ....................... 4 Chapter 2, The Vibrational Spectra of Trimethyliodogermane and Trimethylfluorogermane ............................... 13 Chapter 3, The Preparation of Silicon, Germanium and Tin Primary Arsines Using LiAÂst^)^ ............................... 24 Experimental ........... 25 D i s c u s s i o n ................. ... ....................... 32 Chapter 4, The Preparation of Tertiary and Secondary Silicon A r s i n e s ............................... 37 Experimental ........................... 38 D i s c u s s i o n ............. ......................... .. 51 Chapter 5, The Preparation of Tertiary and Secondary Germanium ,-g Arsines Experimental ........................................... 59 Discussion . ........................................... 73 Chapter 6, The Preparation of Tin A r s i n e s ......................... 82 Experimental .......................................... 83 D i s c u s s i o n ............................................... 91 Chapter 7, Some Reactions of Group IV Ar s i n e s ....................... 96 Experimental ........................................... 99 D i s c u s s i o n .............................................. 108 Chapter 8 , Su m m a r y ...................................... 113 R e f e r e n c e s .............................................. 118 vi Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. List of Figures Figure Page 1 The Infrared Spectrum of Trimethyliodogermane 16 2 The Raman Spectrum of Trimethyliodogermane 17 3 The Infrared Spectrum of Trimethylfluorogermane (4000-1600 cm-1) 19 4 The Infrared Spectrum of Trimethylfluorogermane (1500-400 cm'1 20 5 The Raman Spectrum of Trimethylfluorogermane 21 6 The Infrared Spectrum of Trimethylgermaylarsine 35 vii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. List of Tables Table Page 1 Silicon, Germanium and Tin Arsines Prepared Prior to 1968 2 1.1 Slush Baths 6 2.1 The Vibrational Spectra of (CH^Gel 15 2.2 The Vibrational Spectra of (CH ) „GeF 18 3.1 Syntheses of the Arsines 26 3* 2 Infrared Spectra of the Arsines 27 3.3 . N.m.r. Spectra of Group IV Primary Arsines 28 3.4 Molecular Weights and Cleavage Reactions of the Primary Arsines 29 3.5 Reactions of Silylarsine 31 4.1 Infrared Spectra of the Methtlated Silylarsines 43 4.2 Infrared Spectra of the Silyl(methyl)arsines 44 4.3 Infrared Spectrum of Trimethylsilyl(methyl)arsine 45 4.4 Infrared Spectra of the Silyl(trimethylsilyl)arsines 46 4.5 Infrared Spectra of the Silicon(phenyl)arsines 47 4.6 N.m.r. Spectra of the Silicon Arsines 49 4.7 Molecular Weights, Cleavage and Hydrolyses Reactions of the Silicon Arsines 50 5.1 Infrared Spectra of the Secondary Germanium Arsines 66 5.2 Infrared Spectra of the Methylated Germylarsines 67 5.3 Infrared Spectra of the Germyl(methyl)arsines 68 5.4 Infrared Spectra of the German!um(phenyl)arsines 69 5.5 N.m.r. Spectra of the Germanium Arsines 71 5.6 Molecular Weights and Cleavage Reactions of the Germanium Arsines 72 viii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. List of Tables (continued) Table Page 5.7 Bond Energies 76 6.1 Infrared Spectra of the Tin Arsines 88 6.2 N.m.r. Spectra of the Tin Arsines and Other Trimethyl- stannyl Derivatives 89 6.3 Molecular Weights and Cleavage Reactions of the Tin Arsines 90 7.1 Molecular Weights and Cleavage Reactions of the

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