Chan, Ka Po. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references. / Abstracts in English and Chinese. / Table of contents --- p.vi / Acknowledgements --- p.i / Abstract --- p.ii / 摘要 --- p.iv / List of Compounds Synthesized --- p.xi / Abbreviation --- p.xii / Chapter Chapter 1 --- Synthesis and characterization of pyrazyl-Iinked bis(phosphoranoimido) main group 14 and 13 metal complexes / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.1.1 --- A general review of phosphoranoimine ligands --- p.1 / Chapter 1.1.2 --- A general review of group 14 metal complexes containing phosphoranoimine ligands --- p.8 / Chapter 1.1.3 --- A general review of group 13 metal complexes containing phosphoranoimine ligands --- p.10 / Chapter 1.2 --- Objectives --- p.12 / Chapter 1.3 --- Results and Discussion --- p.14 / Chapter 1.3.1.1 --- Synthesis of pyrazyl-Iinked bis(phosphoranoimine) (Me3SiN=PPr'2CH2)2C4H2N2-2，3 (35) and dilithium compound [{Li(THF)2(Me3SiNPPr'2CH)}2C4H2N2-2，3}] (36) --- p.14 / Chapter 1.3.1.2 --- Spectroscopic properties of 35 and 36 --- p.15 / Chapter 1.3.1.3 --- "Molecular structure of [{Li(THF)2(Me3SiNPPr'2CH)}2C4H2N2-2,3}] (36)" --- p.16 / Chapter 1.3.2.1 --- Synthesis of stannacyclopentane [Sn{C(H)(Pr')2P=N(SiMe3)}2C4H2N2-2，3] (37) and chlorostannylene [{Sncl(Me3SiNPPr'2CH)}2C4H2N2-2，3] (38) --- p.20 / Chapter 1.3.2.2 --- Spectroscopic properties of 37 and 38 --- p.20 / Chapter 1.3.2.3 --- "Molecular structures of [Sn{C(H)(Pr')2P=N(SiMe3)}2C4H2N2-2,3] (37) and [{SnCl(Me3SiNPPr'2CH)}2C4H2N2-2,3] (38)" --- p.22 / Chapter 1.3.3.1 --- "Synthesis of asymmetric lead(II) enamido and chloro compound [{PbCl(Me3SiNPPr'2CH)}C4H2Nr2，3-(CHPPr'2Me3SiN)Pb(Me3SiN PPr'2C)C4H2N2-2,3-(CHPr'2P=NSiMe3)] (39)" --- p.28 / Chapter 1.3.3.2 --- Spectroscopic properties of 39 --- p.30 / Chapter 1.3.3.3 --- "Molecular structure of [{Pbcl(Me3SiNPPr'2CH)}C4H2N2-2,3-(CHPPr'2Me3SiN)Pb(Me3SiN PPr'2C)C4H2N2-2，3-(CHPr'2P=NSiMe3)] (39)" --- p.30 / Chapter 1.3.4.1 --- Synthesis of polymeric dilithiated cyclic germylene [Ge{C(Pr')2PN(SiMe3)Li(THF)}2(02C4H8)C4H2N2-2，3] (40) --- p.35 / Chapter 1.3.4.2 --- Spectroscopic properties of 40 --- p.37 / Chapter 1.3.4.3 --- Molecular structure of [Ge{C(Pr')2PN(SiMe3)Li(THF)}2(02C4H8)C4H2N2-2，3] (40) --- p.37 / Chapter 1.3.5.1 --- "Synthesis of bis(trimethylsilyl)amido metal compounds [{Sn{N(SiMe3)2}(Me3SiNPPr'2CH)}2C4H2N2-2,3] (41) and [{Pb{N(SiMe3)2}(Me3SiNPPr'2CH)} C4H2N2-2，3{Pb(CHPr'2P= NSiMe3){N(SiMe3)2}}](42)" --- p.41 / Chapter 1.3.5.2 --- Spectroscopic properties of 41 and 42 --- p.42 / Chapter 1.3.5.3 --- Molecular structures of [{Sn{N(SiMe3)2}(Me3SiNPPr'2CH)}2C4H2N2-2，3] (41) and [{Pb{N(SiMe3)2}(Me3SiNPPr'2CH)}C4H2Nr2，3{Pb(CHPr'2P= NSiMe3){N(SiMe3)2}}](42) --- p.43 / Chapter 1.3.6.1 --- "Synthesis of pyrazyl-linked bis(phosphoranoimido) group 13 metal compounds [{MCl2(Me3SiNPPr'2CH)}2C4H2N2-2，3] (M=A1 (43)， Ga (44)) and [{AlMe2(Me3SiNPPr'2CH)}2C4H2N2-2,3] (45)" --- p.49 / Chapter 1.3.6.2 --- "Spectroscopic properties of 43, 44 and 45" --- p.50 / Chapter 1.3.6.3 --- "Molecular structures of[{MCl2(Me3SiNPPr'2CH)}2C4H2N2-2,3] (M=A1 (43), Ga (44)) and [{AlMe2(Me3SiNPPr'2CH)}2C4H2N2-2,3] (45)" --- p.50 / Chapter 1.4 --- Experimental Section --- p.57 / Chapter 1.5 --- References for chapter 1 --- p.67 / Chapter Chapter 2 --- Reactivity of pyrazyl-Iinked bis(phosphoranoimido) heteroleptic stannylenes / Chapter 2.1 --- Introduction --- p.73 / Chapter 2.1.1 --- A general review of heteroleptic stannylenes --- p.73 / Chapter 2.2 --- Objectives --- p.80 / Chapter 2.3 --- Results and Discussion --- p.81 / Chapter 2.3.1.1 --- "Reaction of 38 with sodium cyclopentadienide: synthesis of [{Sn(η1-C5H5)(Me3SiNPPr'2CH)}2C4H2N2-2,3] (70)" --- p.81 / Chapter 2.3.1.2 --- Spectroscopic properties of 70 --- p.81 / Chapter 2.3.1.3 --- "Molecular structure of [{Sn(η1-C5H5)(Me3SiNPPr'2CH)}2C4H2N2-2,3] (70)" --- p.83 / Chapter 2.3.2.1 --- "Reaction of 41 with 3,5-di-tert-butyl-o-benzoquinone: synthesis of [{Sn{0(2,4-di-Bu1-C6H2)0}{N(SiMe3)2}(Me3SiNPPr'2CH)}2 C4H2N2-2,3] (71)" --- p.86 / Chapter 2.3.2.2 --- Spectroscopic properties of 71 --- p.87 / Chapter 2.3.2.3 --- "Molecular structure of [{Sn{0(2´ة4-di-Bu'-C6H2)0}{N(SiMe3)2}(Me3SiNPPr'2CH)}2 C4H2N2-2,3] (71)" --- p.88 / Chapter 2.4 --- Experimental Section --- p.91 / Chapter 2.5 --- References for chapter 2 --- p.93 / Chapter Chapter 3 --- "Synthesis, characterization and catalytic study of pyrazyl-linked bis(phosphoranoimido) group 4 early transition metal complexes" / Chapter 3.1 --- Introduction --- p.96 / Chapter 3.1.1 --- A general review of group 4 early transition metal complexes containing phosphoranoimine ligands --- p.96 / Chapter 3.1.2 --- A general review of olefin polymerization with group 4 metallocene catalysts --- p.99 / Chapter 3.2 --- Results and Discussion --- p.101 / Chapter 3.2.1.1 --- "Synthesis and characterization of pyrazyl-linked bis(phosphoranoimido)chloro group 4 transition metal compounds [{MCl3(Me3SiNPPr'2CH)}2C4H2N2-2,3] [M = Zr (72)，Hf (73)]" --- p.101 / Chapter 3.2.1.2 --- Spectroscopic properties of 72 and 73 --- p.101 / Chapter 3.2.1.3 --- "Molecular Structure of [{HfCl3(Me3SiNPPr'2CH)}2C4H2N2-2,3] (73)" --- p.102 / Chapter 3.2.2.1 --- "Synthesis and characterization of pyrazyl-linked bis(phosphoranoimido)amido group 4 transition metal compounds [μ-M(NMe2)2(Me3SiNPPr'2CH)C4H2N2-2,3(CHPPr'2NSiMe3) M(NMe2)3]2 [M = Zr (74), Hf (75)]" --- p.105 / Chapter 3.2.2.2 --- Spectroscopic properties of 74 and 75 --- p.106 / Chapter 3.2.2.3 --- "Molecular Structure of [μ-Zr(NMe2)2(Me3SiNPPr'2CH)C4H2N2- 2,3(CHPPr'2NSiMe3)Zr(NMe2)3]2 (74)" --- p.107 / Chapter 3.2.3.1 --- Catalytic studies of compounds 72-75 on ethylene polymerization --- p.110 / Chapter 3.3 --- Experimental Section --- p.112 / Chapter 3.4 --- References for chapter 3 --- p.116 / Appendix I / Chapter A. --- General Procedures --- p.118 / Chapter B. --- Spectroscopic and physical measurements --- p.118 / Appendix II / Table A.1. Selected crystallographic data for compounds 36-39 --- p.121 / Table A.2. Selected crystallographic data for compounds 40-43 --- p.122 / "Table A.3. Selected crystallographic data for compounds 44, 45, 70 and 71" --- p.123 / Table A.4. Selected crystallographic data for compounds 73 and 74 --- p.124

Glyoxalase II is one of two metalloenzymes found in the glyoxalase pathway and is responsible for catalyzing the hydrolysis of a thioester substrate. Its bimetallic active site is found to contain a variety of metal combinations, including Fe(III)Zn(II). A recent report indicates that human glyoxalase II, while containing a Fe(II)Zn(II) center, is catalytically active as a mononuclear Zn(II) enzyme. Detailed mechanistic studies of glyoxalase II enzymes are limited due to uncertainty in the metal ion content of recombinantly prepared samples. The research presented in this thesis is focused on gaining mechanistic insight into thioester hydrolysis promoted by well-characterized metal complexes The initial research is focused on studies involving a Fe(III)Zn(II) complex supported by the 2-{[bis(2-pyridylmethyl)amino]methyl}-6-[{[2-hydroxyphenyl)methyl]-(2- pyridylmethyl)amino}methyl]-4-methylphenol) ligand. Thioester hydrolysis reactions were examined by following the loss of a deuterium-labeled thioester (hydroxyphenyl thioacetic acid S-methyl(d3) ester) over time using 2H NMR as the monitoring method. Based on kinetic data and spectroscopic investigations (UV-vis and EPR), a reaction pathway for thioester hydrolysis promoted by the aforementioned Fe(III)Zn(II) complex has been proposed. An important feature of this pathway is the formation of a precursor complex wherein the deprotonated α-hydroxy group of the thioester coordinates to the Zn(II) center prior to nucleophilic attack by an Fe(III)-OH moiety. Of relevance to human glyoxalase II, the thioester hydrolysis reactivity of a mononuclear zinc complex containing the N,N-bis(2-pyridylmethyl)-tert-butylamine ligand, (bpta)Zn](ClO4)2⋅0.5H2O, has been examined. Based on kinetic data, it is proposed that thioester hydrolysis promoted by this complex proceeds via a bimolecular pathway, with a Zn-OH moiety being the nucleophile for attack on the thioester carbonyl. Activation parameters are reported for the zinc complex-promoted thioester hydrolysis reaction and are compared to those of OH- promoted thioester hydrolysis reactions. In a separate area of investigation, the chromium chloride complex {(C6H11N2)[CrCl3]}n has been isolated and characterized by elemental analysis and X-ray crystallography. This complex has been proposed as the catalyst responsible for high yield conversion of glucose to 5- hydroxymethylfurfural (HMF), which is an important reaction toward using renewable resources as feedstock chemicals.

Thesis (M.A.)--University of North Carolina at Wilmington, 2006. / Includes bibliographical references (leaves: 96-97)

Thesis (Ph. D.)--University of Hong Kong, 2006. / Title from title frame. Also available in printed format.

The Complexes {[O3P]AlMe}Ag and {[O3P]AlMe}Tl have been synthesized and characterized successfully. The structures of {[O3P]AlMe}Ag and {[O3P]AlMe}Tl were compared with the reported {[O3P]AlMe}Li(DME)3. The 31P NMR showed that soft nature of Ag and Tl ions in {[O3P]AlMe}Ag and {[O3P]AlMe}Tl respectively is interacted with P atom of phenolato ligand and the hard Li ion did not interact with P atom. The reaction of H3[O3P] with YCl3 at RT gave [O3PH]YCl. This is confirmed by 1H NMR technique. The complexes {[O3P]Zn}2Zn(THF)2 and {[OPO]Zn}2 were prepared by the reaction of Zn salt with [O3P]3- and [OPO]2- respectively in excellent yield and characterized by 1H NMR spectroscopy. The X-ray structure of complex {[O3P]Zn}2Zn(THF)2 reveals that it is formed as trimer. We have prepared two thallium complexes derived from diarylamido-based PNP ligands and TlOTf. 31P{1H} NMR revealed that two phosphine atoms in PNP ligand is coordinated with metal Tl center. The palladium-catalyzed aryl amination of 1-bromo-2-chlorobenzene with 2,6-diiso- propylaniline quantitatively produces N-(2-chlorophenyl)-2,6-diisopropylaniline, H[iPrAr- NCl]. Deprotonation of H[iPrAr-NCl] with 1 equiv of n-BuLi in toluene at -35 ¢XC produced cleanly [iPrAr-NCl]Li. Subsequent recrystallization of [iPrAr-NCl]Li in diethyl ether generated the bis(ether) adduct [iPrAr-NCl]Li(OEt2)2. An X-ray study of [iPrAr-NCl]Li- (OEt2)2 showed it to be a four-coordinate species with the coordination of the chlorine atom to the lithium center.

Thesis (Ph. D.)--University of Washington, 2000. / Vita. Includes bibliographical references (leaves 179-189).

Thesis (Ph. D.)--Lehigh University, 2000. / Includes bibliographical references and vita.

Thesis (Ph. D.)--University of Washington, 2001. / Vita. Includes bibliographical references (leaves 144-149).

Thesis (Ph. D.)--University of Hong Kong, 2010. / Includes bibliographical references (leaves 258-281). Also available in print.

Thesis (Ph. D.)--Hong Kong University of Science and Technology, 2003. / Includes bibliographical references (leaves 275-290). Also available in electronic version. Access restricted to campus users.