thesis

Syntheses, structures and reactivities of bis(1-aza-allyl) and bis(phosphoranoimido) metal complexes.

Abstract

Queenie Wai Yan Ip.Thesis (M.Phil.)--Chinese University of Hong Kong, 2003.Includes bibliographical references (leaves 91-94).Abstracts in English and Chinese.Acknowledgements --- p.iiAbstract --- p.iii摘要 --- p.vList of Abbreviations --- p.xiiList of Compounds Synthesized --- p.xiiiChapter CHAPTER 1 --- Syntheses and Characterizations of Pyrazyl-Linked Bis(l-Aza-Allyl) Alkali-Metal ComplexesChapter 1.1. --- Introduction --- p.1Chapter 1.1.1. --- A General Review of 1-Aza-Allyl Ligands --- p.1Chapter 1.1.2. --- A General Review of Group 1 Alkali-Metal Complexes Containing Bis(l-Aza-Allyl) Ligands --- p.6Chapter 1.2. --- Objective --- p.9Chapter 1.3. --- Results and Discussion --- p.11Chapter 1.3.1. --- Preparation and Characterization of Pyrazyl-Linked Bis(l-Aza-Allyl) Di-Lithium Complex --- p.11Chapter 1.3.1.1. --- "A Modified Synthesis of Pyrazyl-Linked Bis(l-Aza-Allyl) Di-Lithium Complex [Li2{{N(SiMe3)C(But)C(H)}2C4H2N2-2,3}(THF)2]2 (1)" --- p.11Chapter 1.3.1.2. --- Physical and Spectroscopic Properties of Complex 1 --- p.11Chapter 1.3.1.3. --- Molecular Structure of Complex 1 --- p.12Chapter 1.3.2. --- Preparation and Characterization of Pyrazyl-Linked Bis(l-Aza-Allyl) Di-Sodium and Di-Potassium Complexes --- p.15Chapter 1.3.2.1. --- "Preparation of Pyrazyl-Linked Bis( 1 -Aza-Allyl) Di-Sodium complex [Na2{{N(SiMe3)C(But)C(H)}2C4H2N2-2,3}(THF)2]2 (2) and Di-Potassium Complex [K2{{N(SiMe3)C(But)C(H)}2C4H2N2-2,3}- (THF)3]2 (3)" --- p.15Chapter 1.3.2.2. --- Physical and Spectroscopic Properties of Complexes 2 and 3 --- p.15Chapter 1.3.2.3. --- Molecular Structures of Complexes 2 and 3 --- p.16Chapter 1.4 --- Experimental Section --- p.23Chapter 1.5 --- References --- p.25Chapter CHAPTER 2 --- Syntheses and Characterizations of Pyrazyl-Linked Bis(l-Aza-Allyl) Group 2 and 12 Metal ComplexesChapter 2.1 --- Introduction --- p.29Chapter 2.1.1. --- A General Review of Group 2 Metal Complexes containing Bis(l-Aza-Allyl) Ligands --- p.29Chapter 2.1.2. --- A General Review of Group 12 Metal Complexes containing Bis(l-Aza-Allyl) Ligands --- p.32Chapter 2.2 --- Results and Discussion --- p.34Chapter 2.2.1. --- Preparation and Characterization of Pyrazyl-Linked Bis(l-Aza-Allyl) Di-Magnesium Complex --- p.34Chapter 2.2.1.1. --- "Preparation of Pyrazyl-Linked Bis(l-Aza-Allyl) Di-Magnesium Complex [Mg2{{N(SiMe3)C(But)C(H)}2C4H2N2-2,3}Br2(THF)4] (4).……" --- p.34Chapter 2.2.1.2. --- Physical and Spectroscopic Properties of Complex 4 --- p.34Chapter 2.2.1.3. --- Molecular Structure of Complex 4 --- p.35Chapter 2.2.2. --- Preparation and Characterization of Pyrazyl-Linked Bis(l-Aza-Allyl) Lithium Zincate Complex --- p.38Chapter 2.2.2.1. --- "Preparation of Pyrazyl-Linked Bis(l-Aza-Allyl) Lithium Zincate Complex [Zn2{{N(SiMe3)C(But)C(H)}2C4H2N2-2,3}Cl2(u-Cl)2Li2(THF)6] (5)" --- p.38Chapter 2.2.2.2. --- Physical and Spectroscopic Properties of Complex 5 --- p.39Chapter 2.2.2.3. --- Molecular Structure of Complex 5 --- p.39Chapter 2.2.3. --- Preparation and Characterization of Unexpected Cyclization Compound --- p.42Chapter 2.2.3.1. --- "Preparation of Unexpected Cyclization Compound [{Me2Si{NC(But)C(H)}}2C4H2N2-2,3] (6)" --- p.42Chapter 2.2.3.2. --- Physical and Spectroscopic Properties of Complex 6 --- p.43Chapter 2.2.3.3. --- Molecular Structure of Complex 6 --- p.44Chapter 2.2.4. --- Attempted Synthesis of Analogous Mercury Complex --- p.45Chapter 2.2.5. --- Comparison on Structures and Reactivities of Compounds 4-6 --- p.46Chapter 2.3. --- Experimental Section --- p.48Chapter 2.4. --- References --- p.50Chapter CHAPTER 3 --- Syntheses and Characterizations of Bis(Phosphoranoimido) Magnesium and Group 14 Metal ComplexesChapter 3.1 --- Introduction --- p.52Chapter 3.1.1. --- A General Review of Functionalized Phosphoranoimine Ligands --- p.52Chapter 3.1.2. --- A General Review of Group 14 Metal Complexes Containing Bis(Phosphoranoimines) Ligands --- p.59Chapter 3.2. --- Objective --- p.61Chapter 3.3. --- Results and Discussion --- p.64Chapter 3.3.1. --- Preparation and Characterization of Bis(Phosphoranoimido) Magnesium Complexes --- p.64Chapter 3.3.1.1. --- "Preparation and Characterization of Bis(Phosphoranoimido) Magnesium Complexes [Mg{(Me3SiN=PR2CH)2C5H3N-2,6}THF] (R = Pri, 9; R = Ph, 10)" --- p.64Chapter 3.3.1.2. --- Physical and Spectroscopic Properties of Complexes 9 and 10 --- p.64Chapter 3.3.1.3. --- Molecular Structures of Complexes 9 and 10 --- p.65Chapter 3.3.2. --- Preparation and Characterization of Bis(Phosphoranoimido) Tin(II) and Lead(II) Complexes --- p.70Chapter 3.3.2.1. --- "Preparations and Characterizations of 1,3-Distannacyclobutane with Chlorotin(II) Alkyl Complex [{2-{Sn{C(Pri2P=NSiMe3)}}-6- {Sn{CH(Pri2p=NSiMe3)}Cl}}C5H3N]2 (11) and 1,3-Diplumbacyclobutane with bis(trimethylsilyI)amido Lead(II) Alkyl Complex [{2-{Pb{C(Pri2P=NSiMe3)}}-6-{Pb{CH(Pri2P=NSiMe3)}N(SiMe3)2}}- C5H3N]2 (12)" --- p.70Chapter 3.3.2.2. --- Physical and Spectroscopic Properties of Complexes 11 and 12 --- p.73Chapter 3.3.2.3. --- Molecular Structures of Complexes 11 and 12 --- p.74Chapter 3.3.3. --- Preparation and Characterization of Bis(Phosphoranoimido) Germanium(II) Enamido and Alkyl Complex --- p.79Chapter 3.3.3.1. --- Preparation and Characterization of Bis(Phosphoranoimido) Germanium(II) Enamido and Alkyl Complex [{2-CH(Pri2P=NSiMe3)-6-CH(Pri2P=NSiMe3)}C5H3NGe{2-{C(Pri2P=NSi Me3)Ge} -6-CH2(Pri2P=NSiMe3)} C5H3N] (13) --- p.79Chapter 3.3.3.2. --- Physical and Spectroscopic Properties of Complex 13 --- p.81Chapter 3.3.3.3. --- Molecular Structure of Complex 13 --- p.81Chapter 3.3.4. --- Comparison on Structures and Reactivities of Compounds 11-13 --- p.85Chapter 3.4. --- Experimental Section --- p.87Chapter 3.5. --- References --- p.91APPENDIX IChapter A --- General Experimental Procedures and Physical Measurement --- p.95Chapter B --- X-Ray Crystallography --- p.96APPENDIX IITables of Crystallographic Data and Refinement Parameters --- p.9

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