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Gas Phase Chemistry of Organic Anions Involving Isomerisation

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Gas Phase Chemistry of Organic Anions Involving Isomerisation a\t.3.92 o A Gas Phase Chemistry of Organic Anions involviog Isomerisatíon A Thesis submitted for the Degree of Doctor of Philosophy in the Department of Organic Chemistry by Kevin M. Downard B.Sc. (Hons.) Tl-re University of Adelaide luly,7997 "No amount of experimentation can ever prove me right; a single experiment can prove me wrong." Alb ert Einstein (787 9 -19 55) I Contents Statement Page viii Acknowledgements ix Figures xi Tables xiii Abstract xvi Chapter 1 An introduction to negative ion mass spectrometry 1 1.1 Introduction 1 7.2 Negative ion generation by direct electron capture 2 7.2.7 Associative resonance capture 2 1..2.2 Dissociative resonance capture 3 1,.2.3 lon-pair production 3 1.3 Negative ion chemical ionisation 4 1.3.1 Proton transfer 4 7.3.2 Nucleophilic displacement 5 1.3.3 Nucleophilic addition 5 7.3.4 Charge transfer 5 7.4 A double sector reverse-geometry mass spectrometer 6 7.4.7 Collisional activation mass analysed kinetic energy spectra 8 l1 7.4.2 The fragmentations of even-electron organic anions on collisional activation 9 7.4.2.1, Simplehomolytic cleavage 9 7.4.2.2 Fragmentations through an ion-molecule complex 9 7.4.2.3 Rearrangements 10 1,.4.2.4 Chargeremotefragmentations 10 7.4.3 Charge reversal mass spectra 11 1.5 A triple sector mass spectrometer 12 7.6 Ab initío molecular orbital calculations - a theoretical aid to studies of gas-phase ion chemistry 1.4 1,.6.7 Introduction 74 7.6.2 Electronic and nuclear motion 15 1,.6.3 Molecular orbital theory 16 7.6.4 Møller-Plesset perturbation theory 79 1.6.5 Nomenclature 20 1..7 Gas phase ion-molecule chemistry 27 7.7.1, Introduction 21. 7.7.2 The flowing afterglow - S.I.F.T. instrument 23 7.7.2.7 Collision-induced dissociation in the S.I.F.T. instrument 24 1.7.2.2 Gas-phase aciditymeasurements 24 7.7.2.3 Reaction rates and branching ratios 26 7.7.2.4 lon-molecule reaction efficiencies 29 Chapter 2 cr and p substituted alkyl carbanions in the gas phase 30 2.7 Introduction 30 111 2.2 c¡-Substituted carbanions 32 2.2.7 Gas-phase experiments to generate carbanions RXCH2- 33 2.2.2 The hydroxymethylene anion 38 2.2.2.1, Theoretical considerations to the possible detection of the hydroxymethylene anion 38 2.2.2.2 The attempted formation of the hydroxymethylene anion 40 2.2.3 The methylene thiol anion 42 2.2.3.7 Theoretical considerations concerning the possible detection of the methylene thiol anion 42 2.2.3.2 Formation of the methylene thiol anion 43 2.2.3.3 The reactivity of the methylene thiol anion 49 2.2.3.3.1, Experimental determination of the proton affinity of HSCHz 52 2.2.3.3.2 Reactions of HSCH2- involving hydride ion transfer 53 2.2.3.4 Thermochemistry of the methylene thiol anion 59 2.2.4 The amino methylene anion 60 2.2.4.7 Theoreticalconsiderations concerningthepossible detection of the amino methylene anion 60 2.2.4.2 The attempted gas phase formation of the amino methylene anion 61' 2.2.5 The methylthiomethylene anion 63 2.2.5.7 Theoretical considerations concerning the possible detection of the methylthiomethylene anion 63 2.2.5.2 The formation of the methylthiomethylene anion 63 2.2.6 The methoxymethylene anion 64 2.2.6.7 Theoreticalconsiderations concerningthepossible detection of the methoxymethylene anion 64 1V 2.2.6.2 The attempted gas phase formation of the methoxy- methylene anion 65 2.2.7 The N-methyl amino methylene anion 66 2.2.7.1, Theoretical considerations concerning the possible detection of the N-methyl amino methylene anion 66 2.2.7.2 The attempted gas phase formation of the N-methyl amino methylene anion 67 2.2.8 The N,N-dimethyl amino methylene anion 67 2.2.8.7 Theoretical considerations concerning the possible detection of the N,N-dimethyl amino methylene anion 67 2.2.8.2 The attempted gas phase formation of the N,N-dimethyl amino methylene anion 68 2.3 p-Substitutedcarbanions 69 2.3.7 p-Keto ethyl anions 72 2.3.1,.7 The p-formylethyl anion 72 2.3.1,.2 The p-acetylethyl anion 76 2.3.1,.3 The p-benzoylethyl anion 81 2.3.1,.4 TheB-hydroxycarbonylethyl anion 86 2.3.1,.5 Thep-methoxycarbonylethyl anion 86 2.3.2 The p-vinylethyl anion 88 2.4 Summary and conclusions 93 Chapter 3 The formatiory structure and reactivity of HNzO-. A product ion study. 95 3.1 Introduction 95 v 3.2 The reactivity of HN=NO- in the flowing afterglow 100 3.2.7 Experimental determination of the basicity of HN=NO- 100 3.2.2 Reactions of HN=NO- involving oxidation 702 3.3 Thermochemistry of the HN=NO- ion 1.09 Chapter 4 The elimination of ethene from deprotonated ethyl methyl sulphoxide. The formation, structure and reactivity of the methyl sulphinyl anion. 110 4.'t Introduction 11.0 4.2 Structure elucidation of the (CHgSO)- ion 172 4.3 Reactivity of the (CHgSO)- ion 115 4.3.1. Experimental determination of the basicity of (CHgSO)- 71,6 4.3.2 The reactivity of the methyl sulphinyl anion 118 4.4 Thermochemistry of the methyl sulphinyl anion 126 4.5 Thermochemistry of the loss of ethene from deprotonated ethyl methyl sulphoxide 727 4.6 The methyl disulphide anion 129 4.6.1 Formation of the methyl disulphide anion 129 4.6.2 The reactivity of the methyl disulphide anion 131 4.6.2.1, Experimental determination of the basicity of CH3SS- 131 4.6.2.2 Reactivity of the methyl disulphide anion 131 4.6.3 Thermochemistry of the methyl disulphide anion 1,34 4.7 The formation and reactivity of the formyl sulphinyl anion 134 v1 Chapter 5 Gas phase intramolecula¡ anionic rearrangements involving the migration of silicon 737 5.1 Introduction 137 5.2 Trimethyls ilyl alkoxides 138 5.3 Trimethylsilylalkyl carboxylates 1,47 5.4 Deprotonated trimethylsilyl ketones 1,45 5.4.1, Deprotonated alkoyltrimethylsilanes 146 5.4.2 Deprotonated benzoyltrimethylsilane 752 5.5 Trimethylsilylaryl carboxylates 153 5.6 Trimethylsilylbenzyl carboxylates 158 5.7 Summary and conclusions 762 Summary and conclusions 1,64 Chapter 6 Experimental 1,67 6.7 Instrumentation 767 6.2 Synthesis 170 6.2.1. Commercial samples used for experiments discussed in chapter 2 170 6.2.2 Synthesis of unlabelled compounds for chapter 2 170 6.2.3 Synthesis of labelled compounds for chapter 2 176 6.2.4 Synthesis of compounds for chapter 3 177 6.2.5 Synthesis of compounds for chapter 4 177 vll 6.2.6 Synthesis of unlabelled compounds for chapter 5 178 6.2.7 Synthesis of labelled compounds for chapter 5 183 References 185 Publications 199 #q I l i I / I I n ¡. t- ¡ I I I I .l lx Acknowledgements First and foremost, I would like to thank my supervisor Professor |ohn Bowie for his guidance, tireless enthusiasm and timely assistance and advice throughout my postgraduate studies. More recently, I am indebted to him for suggesting many improvements to this thesis which have greatly improved its quality. I would also like to thank him for providing me with the opportunity to visit The University of Colorado at Boulder to utilise the F.A.-S.I.F.T instrument. This opportunity would not have been possible without the support of Professor Charles DePuy and The University of Colorado. My sincere thanks to Professor DePuy and his entire research group for their kindness and d helpful guidance during my stay. I am particularly grateful to Dr.'s Scott I I rl Gronert and Michelle Krempp for their initial help with the operation of the instrument and to Hilary Oppermann whose assistance throughout my visit was very much appreciated. I gratefully acknowtedge The University of Adelaide for providing financial assistance for my flight to Boulder in the form of a University of Adelaide ì i Travel Grant and a Donald Stranks Travelling Fellowship. I acknowledge i the financial support of a University of Adelaide Postgraduate Scholarship. i t i, I would like to thank Dr. Sheldon for performing the high-level ab ¡. |ohn i¡ T' ti initio calculations presented in this thesis which have provided a valuable I rt ( insight into the chemistry studied. I also thank Dr. Roger Hayes, formerly of { The University of Nebraska, Lincoln, for recording the triple M.S. spectra 4 reproduced in this thesis. Ii I x My thanks to all the members of the Organic Chemistry department for their helpfut advice, assistance and friendship. In particular, I would like to thank the members of the Bowie research group who provided many consÍuctive suggestions regarding my research work during many lively and stimulating group seminars. Finally, I am especially grateful to my family and friends for their support and encouragement throughout my years of study. A special thank you to my parents, Valerie and Michael, for their continual support and for putting up with this sometimes temperamental scientist. My thanks also to my mother for graciously proof-reading this thesis. XI Figures Page 1.1 A schematic representation of a double-focussing mass spectrometer of reverse geometry 7 7.2 Representation of a Kratos M$50 Triple Analyser mass spectrometer exhibiting EBE geometry 13 1.3 An electronic configuration diagram for 16cr1cr)(r)ÞrÞXr)ozcr)(OÞ2p¡1*"ro, 18 7.4 The tandem flowing afterglow-S.I.F.T.-drift instrument 23 2.1, Collisional activation mass spectra of isomeric -CHzSH and CH3S- M 2.2 Charge reversal mass spectra of isomeric -CH2SH and CH3S 45 2.3 Interaction between a doubly occupied p-orbital an an unoccupied o*-orbital of a (C-X) bond 70 2.4 Conformers of a p-substituted ethyl anion in which the hyperconjugation effect is maximised and minimised 70 2.5 The interaction of a p(C-)-orbital and the r orbitals of an adjacent C=O group 76 2.6 C.A.
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