Syntheses, structures and reactivities of bis(thiophosphinoyl) metal complexes.

Abstract

Wan, Chi Ling.Thesis (M.Phil.)--Chinese University of Hong Kong, 2009.Includes bibliographical references.Abstracts in English and Chinese.Table of Contents --- p.viAcknowledgement --- p.iAbstract --- p.ii摘要 --- p.ivList of Compounds Synthesized in This Work --- p.xAbbreviation --- p.xiChapter Chapter 1 --- Synthesis of Group 1 and 2 Metal Bis(thiophosphinoyl) ComplexesChapter 1.1 --- Introduction --- p.1Chapter 1.1.1 --- General Aspects of Thiophosphinoyl Ligands --- p.1Chapter 1.1.2 --- General Aspects of Group 1 and 2 Thiophosphinoyl Metal Complexes --- p.6Chapter 1.1.3 --- Objectives of This Work --- p.10Chapter 1.2 --- Results and Discussion --- p.11Chapter 1.2.1.1 --- Synthesis of Monoanionic Bis(thiophosphinoyl) Lithium Complex --- p.11Chapter 1.2.1.2 --- Spectroscopic Properties of 42 --- p.11Chapter 1.2.1.3 --- Molecular Structure of [Li{(S=PPh2)CH}(THF)(Et20)] (42) --- p.12Chapter 1.2.2.1 --- Synthesis of Dianionic Bis(thiophosphinoyl) Magnesium Complex --- p.14Chapter 1.2.2.2 --- Spectroscopic Properties of 43 --- p.14Chapter 1.2.2.3 --- Molecular Structure of [MgC(PPh2=S)(THF)]2.2THF (43) --- p.15Chapter 1.3 --- Experimental for Chapter 1 --- p.17Chapter 1.4 --- References for Chapter 1 --- p.19Chapter Chapter 2 --- Synthesis and Reactivity of Group 14 Metal Bis(thiophosphinoyl) ComplexesChapter 2.1 --- Introduction --- p.24Chapter 2.1.1 --- General Aspects of Low Valent Group 14 Organometallic Compounds --- p.24Chapter 2.2 --- Results and Discussion --- p.32Chapter 2.2.1.1 --- "Synthesis of 1,3-Distannacyclobutane and 1,3-Diplumbacyclobutane" --- p.32Chapter 2.2.1.2 --- Spectroscopic Properties of 74 and 75 --- p.33Chapter 2.2.1.3 --- Molecular Structures of [Sn{u2-C(Ph2P=S)2}]2.THF (74) and [Pb{u2-C(Ph2P=S)2}]2.THF(75) --- p.34Chapter 2.2.2.1 --- "Reaction of 1,3-Diplumbacyclobutane with Chalcogens" --- p.38Chapter 2.2.2.2 --- Spectroscopic Properties of 78 and 79 --- p.39Chapter 2.2.2.3 --- "Molecular Structures of [PbE{C(PPh2=S)2}] (E = S (78),Se (79))" --- p.39Chapter 2.2.3.1 --- Synthesis of Chlorogermylene and Chlorostannylene --- p.44Chapter 2.2.3.2 --- Spectroscopic Properties of 80 and 81 --- p.44Chapter 2.2.3.3 --- "Molecular Structures of [MCl{CH(PPh2=S)2}] (M = Ge (80),Sn (81))" --- p.45Chapter 2.2.4.1 --- Reaction of Chlorogermylene with Chalcogens --- p.49Chapter 2.2.4.2 --- Spectroscopic Properties of 82 --- p.50Chapter 2.2.4.3 --- Molecular Structure of [GeCl{CH(PPh2=S)2}(u-S)]2.4THF (82) --- p.51Chapter 2.2.4.4 --- Reaction of Chlorostannylene with Pb{N(SiMe3)2}2 --- p.53Chapter 2.3 --- Experimental for Chapter 2 --- p.54Chapter 2.4 --- References for Chapter 2 --- p.60Chapter Chapter 3 --- Synthesis of Group 13 Metal Bis(thiophosphinoyl) ComplexesChapter 3.1 --- Introduction --- p.65Chapter 3.1.1 --- General Aspects of Group 13 Organometallic Chemistry --- p.65Chapter 3.1.2 --- General Aspects of Group 13 Metal Complexes Bearing Phosphoranoimine or Phosphoranosulfide Ligands --- p.67Chapter 3.2 --- Results and Discussions --- p.72Chapter 3.2.1 --- Synthesis of Group 13 Metal Bis(thiophosphinoyl) Complexes --- p.72Chapter 3.2.2 --- Spectroscopic Properties of 108-110 --- p.72Chapter 3.2.3 --- "Molecular Structures of [MCl{C(PPh2=S)2}]2 (M = A1 (108),Ga (109), In (110))" --- p.73Chapter 3.3 --- Experimental for Chapter 3 --- p.79Chapter 3.4 --- References for Chapter 3 --- p.82Chapter Chapter 4 --- Synthesis of Group 4 Metal Bis(thiophosphinoyl) ComplexesChapter 4.1 --- Introduction --- p.86Chapter 4.1.1 --- General Aspects of Group 4 Early Transition Metal Complexes --- p.86Chapter 4.2 --- Results and Discussion --- p.92Chapter 4.2.1 --- Synthesis of Group 4 Metal Bis(thiophosphinoyl) Complexes --- p.92Chapter 4.2.2 --- Spectroscopic Properties of 125-128 --- p.93Chapter 4.2.3 --- Molecular Structures of [Hf(NMe2)3{CH(PPh2=S)2}] (126) --- p.94Chapter 4.3 --- Experimental for Chapter 4 --- p.97Chapter 4.4 --- References for Chapter 4 --- p.100Appendix IChapter A. --- General Procedures --- p.104Chapter B. --- Physical and Analytical Measurements --- p.104Chapter C. --- X-ray Crystallographic Determination --- p.105Appendix II"Table A.1. Selected Crystallographic Data for Compounds 42,43,74 and 75" --- p.108Table A.2. Selected Crystallographic Data for Compounds 77-80 --- p.109"Table A.3. Selected Crystallographic Data for Compounds 81,108-110 and 126" --- p.110Appendix IIIChapter A. --- Future Work --- p.11