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Coversheet for Thesis in Sussex Research Online A University of Sussex DPhil thesis Available online via Sussex Research Online: http://sro.sussex.ac.uk/ This thesis is protected by copyright which belongs to the author. This thesis cannot be reproduced or quoted extensively from without first obtaining permission in writing from the Author The content must not be changed in any way or sold commercially in any format or medium without the formal permission of the Author When referring to this work, full bibliographic details including the author, title, awarding institution and date of the thesis must be given Please visit Sussex Research Online for more information and further details CHEMISTRY OF THE TERMINAL PNICTOGEN COMPLEXES OF LEAD, TIN AND GERMANIUM Lisa Ann Marie Harris DPhil Chemistry University of Sussex October 2012 I hereby declare that this thesis has not been and will not be submitted in whole or in part to another University for the award of any other degree. Signature ……………………………………………………………… UNIVERSITY OF SUSSEX LISA ANN MARIE HARRIS CHEMISTRY OF THE TERMINAL PNICTOGEN COMPLEXES OF LEAD, TIN AND GERMANIUM SUMMARY A series of tin(II) and lead(II) β-diketiminate amides [(BDI)MNRR’] (BDI = [CH{(CH3)CN-2,6-iPr2C6H3}2]; M = Sn, Pb; RR’ = iPr2, H(2,6-iPr2-C6H3), H(2-iPr-C6H4), H(C6H5)) were synthesised and characterised. The reactivity of [(BDI)MN(iPr)2] and [(BDI)MNH(2,6-iPr2-C6H3)] towards aliphatic electrophiles, heterocumulenes and acids was investigated. The lead systems were found to be more reactive than the tin systems and the amide ligand was found to be more reactive than the anilide ligand. In general, the [(BDI)MNRR’] systems under investigation displayed the expected nucleophilic and basic behaviour. For instance, treatment of [(BDI)SnNH(2,6-iPr2-C6H3)] with methyl triflate resulted in the formation of [(BDI)SnOSO2CF3]. However, addition of phenyl isocyanate to [(BDI)MNRR’] (M = Sn, Pb; RR’ = iPr2, H(2,6-iPr2-C6H3)) resulted in the formation of a bis- β-diketiminate complex, [(BDI)M(OC{=NPh}C{=C(Me)CN(H)(Ar)}(C{Me}=CN(Ar)})], a net result of nucleophilic addition to the electrophilic carbon in phenyl isocyanate by the γ- carbon in the BDI backbone. DFT studies were undertaken to rationalise the reactivity. The reactivity of group 14 metal β-diketiminate phosphide complexes [(BDI)MPR2] (BDI = [CH{(CH3)CN-2,6-iPr2C6H3}2]; M = Ge, Sn, Pb; R = C6H11, C6H5) towards selenium and tellurium was examined. For the tin(II) and lead(II) systems, no reactivity was observed upon addition of one or five equivalents of tellurium. In contrast, the germanium(II) systems exhibited unexpected reactivity with selenium and tellurium, where one equivalent of the chalcogen resulted in its insertion into the germanium-phosphorus bond, [(BDI)GeEPR2] (E = Se, Te), and five equivalents of selenium resulted in a further coordination of a selenium to the phosphorus, [(BDI)GeSeP(Se)R2]. DFT studies were undertaken in order to rationalise this behaviour. Lastly, the process of aerosol-assisted chemical vapour deposition (AACVD) was undertaken on some of these group 14 metal chalcogenide complexes in order to probe their suitability as a single source precursor (SSP) for thermo-electric materials. Acknowledgements First and foremost, I would like to thank my supervisor Robin for the opportunity to complete a DPhil in such an amazing lab with so many wonderful colleagues. Robin’s enthusiasm, hard work and brilliance, not to forget her guidance and warmth will always stay with me and has taught me many lessons, both professionally and personally. I feel honoured to have worked with Robin and any pride I feel in my work is a result of Robin’s belief in me and my abilities. I would also like to express my thanks to Martyn and Peter for X-ray crystallography, Iain for help with NMR related issues, Ali for mass-spectroscopy and Qiao for microscopy. I would also like to thank Mick for all the items I was allowed to ‘borrow’ from the teaching labs. I must impart a warm thanks to all my wonderful colleagues I had the pleasure to work with over the years for all the great times we shared both inside and outside the lab, especially to Eric, Morgan, Lorenzo, Mat and Luke. To Eric, my friend and colleague, I must express sincere gratitude for all his help and advice over the years and who I have the greatest respect for. I am grateful to my friends Sarah and Donna who have not only been supportive but kept me sane. To Sarah I would like to thank her for our conversations – your constancy and sunny disposition have always made your company so pleasurable. To Donna I would like to thank her for introducing me to the benefits of running and who I owe my past and any future sub-20 5K times to. I am extremely grateful to all my family for being so supportive of me over the years. My most sincere gratitude goes towards my mother, Ann, who has put up with my tantrums and not only bore them well but acted as one of the finest (unpaid) psychiatrists anyone could wish to have. Furthermore, I would also like to thank my cats (past and present) Josie, Susie and Sheba for providing many hours of light hearted moments! Special mention must also be given to my grandfather, Panayiotis, for all his support, assistance and enthusiasm. Without his help I doubt this thesis could have been written. I am also grateful to my uncle Ken (and his partner Theresa) for always being there, from the very beginning to the end, my uncle Nicholas and my brother, Michael. i Table of Contents List of Figures, Schemes and Tables IV List of Abbreviations XII Chemistry of the terminal pnictogen complexes of lead, tin and germanium. 1. Introduction 2 1.1. History of the Ge, Sn and Pb 2 1.2. Recent advances in divalent organotetrylene chemistry 4 1.2.1. β-diketiminate 14 1.2.1.1. Structural studies 24 1.2.2. Summary 25 1.3. Aims 26 2. Group 14 metal amides: synthesis and reactivity studies 27 2.1. Overview of late transition metal amide chemistry 27 2.2. Synthetic procedures 28 2.3. Reactivity studies 31 2.3.1. Nucleophilic reactivity with unsaturated organic 31 electrophiles 2.3.2. Reaction with carbon monoxide 35 ii 2.3.3. Basic reactivity with weak acids 40 2.4. Overview of group 14 metal amide chemistry 45 2.4.1. Reactivity studies 45 2.5. β-diketiminate Sn(II) and Pb(II) amide and anilide synthesis and 52 characterisation 2.5.1. β-diketiminate stannylene amide and anilide synthesis and 52 characterisation 2.5.2. β-diketiminate plumbylene amide and anilide synthesis and 61 characterisation 2.5.3. Summary of stannylene and plumbylene amide complexes 73 2.6. Reactivity studies on β-diketiminate Sn(II) and Pb(II) amide and 74 anilide complexes 2.6.1. Reactivity of β-diketiminate stannylene amide and anilide 74 complexes towards aliphatic electrophiles 2.6.2. Reactivity of β-diketiminate stannylene amide and anilide 75 complexes towards unsaturated electrophiles 2.6.3. Reactivity of β-diketiminate stannylene amide and anilide 83 complexes towards carboacids 2.6.4. Reactivity of β-diketiminate plumbylene amide and anilide 87 complexes towards aliphatic electrophiles 2.6.5. Reactivity of β-diketiminate plumbylene amide and anilide 90 complexes towards unsaturated electrophiles iii 2.6.6. Reactivity of β-diketiminate plumbylene amide and anilide 96 complexes towards carboacids 2.6.7. Summary of the reactivity of stannylene and plumbylene 97 amide complexes 2.7. Computational studies on β-diketiminate Sn(II) and Pb(II) amide and 98 anilide complexes 3. Group 14 metal phosphides: reactivity studies 106 3.1. Recent advances in the multiple bonded chalcogenide complexes of the 106 germanium, tin and lead elements 3.1.1. Summary of β-diketiminate group 14 metal phosphide 118 reactivity 3.2. Recent advances in group 14 metal chalcogenides as single source 121 precursors (SSPs) for chemical vapour deposition (CVD) 3.3. Reactivity studies on β-diketiminate group 14 metal phosphides 125 3.3.1. β-diketiminate group 14 metal phosphide synthesis 125 3.3.2. The reactivity of β-diketiminate group 14 metal phosphides 126 with chalcogens 3.3.3. The reactivity of β-diketiminate group 14 metal phosphides 138 with excess chalcogen 3.3.4. Summary of β-diketiminate group 14 metal phosphides 143 3.4. Computational studies on β-diketiminate Ge(II) phosphide complexes 145 iv 3.5. Chemical material studies on β-diketiminate group 14 metal 152 phosphides 3.5.1. Summary of AACVD studies 162 4. Summary of the chemistry of the terminal pnictogen complexes of lead, tin and 163 germanium 5. Experimental 167 5.1. General considerations 167 5.2. Computational details 168 5.3. Synthetic methods 168 5.4. Materials chemistry 183 5.5. NMR parameters 185 5.6. Crystallographic data 186 6. References 200 Supplementary data - Crystallographic data, NMR spectra and Gaussian (.log and CD-ROM .chk) files List of Figures, Schemes and Tables Figure 1 Examples of group 14 metal terphenyl complexes (M = Ge, Sn, Pb). 6 Figure 2 Five-membered N-heterocyclic carbene ligand system (R = dipp, iPr, 6 v Mes; R’ = H, Me). Figure 3 Zwitterionic carbene plumbylene complex (Ar’ = 2,6-iPr2-C6H3). 7 Figure 4 Five-membered N-heterocyclic ring (M = Ge, Sn, Pb). 8 Figure 5 Diphosphide germanium and tin complexes (M = Ge, Sn; R = 11 (Me3Si)2CH). Figure 6 Four-membered N-heterocyclic ring (M = Ge, Sn; R = NHR, Cl, OH 12 (Sn)). Figure 7 Oxygen-bridged dimeric lead amidinate complex (Ar’ = 2,6-iPr2-C6H3).
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