Chapter 1 provides the general review of phosphoranoimines and 1-azaallyls as ligands for group 4 and 14 metal complexes. / Chapter 2 describes the development of low-valent group 14 1,3-dimetallacyclobutanes from phosphoranoimines. Three low-valent 1,3-distannacyclobutanes 1,3-[Sn{C(Pr i2P=NSiMe3)(2-Py)}]2 ( 95), 1,3-[Sn{C(Ph2P=NSiMe3)(C6H 5)}]2 (97) and 1,3-[Sn{C(Ph2P=NSiMe 3)(PPh2)}]2 (100) were synthesized from the phosphoranoimine ligands [CH2(Pri 2P=NSiMe3)(2-Py)] (92), [CH2(Ph 2P=NSiMe3)(C6H5)] (96) and [CH2(Ph2P=NSiMe3)(PPh 2)] (99), respectively. A novel cationic tin(IV) species [HC(Pri2P=NSiMe3)(Ar)] -[SnCl3]+ (Ar = 9-anthryl) ( 104) was synthesized from [CH2(Pri 2P=NSiMe3)(Ar)] (Ar = 9-anthryl) (103). / Chapter 3 describes the reactivies of low-valent group 14 1,3-distannacyclobutanes (95 and 111) and the isolation of the enantiomers of 95 and [1-Sn{C(Pri2P=NSiMe 3)(2-Py)}3-Pb{C(Pri2P=NSiMe 3)(2-Py)}] (120). The reactions of 95 or 111 with M(CO)5(THF) (M = Cr, Mo, W), CpMn(CO)2THF (Cp = eta-C5H5), MeI and Br2 were performed. Three isomers of compound 95 (95R, 95S and 95I) and two enantiomers of compounds 120 ( 120R and 120S) and 122 (122R and 122S) were obtained by the method of recrystallization from different solvents. Heteroleptic lead(II) compound [{(Pri 2P=NSiMe3)(2-Py)CH}Pb{N(SiMe3)2} 2] (121) was synthesized, which further react with 94 to give 1,3-[Pb{C(Pri2P=NSiMe 3)(2-Py)}]2 (122). / Chapter 4 describes the development of group 4 metal complexes from phosphoranoimines. Group 4 metal imido complexes [(Me2N)2M{CH(Ph2 PN)(2-Py)}]2 (M = Zr (133), Hf (134)) and ionic compounds [ML2Cl]+2[MCl 6]2- (L = {CH(R2PNSiMe3)(2-Py)}) (135 M = Zr, R = Ph, 136 M = Hf, R = Ph, 137 M = Zr, R = Pri, 138 M = Hf, R = Pri) were synthesized. The neutral zirconium(IV) dichloride compound [ZrCl2{CH(Ph2P=NSiMe 3)(C6H5)}2] (139) was prepared by the reaction of lithium compound [(THF)2Li{CH(Ph 2PNSiMe3)(C6H5)}] (97) with ZrCl4. The catalytic activity of the compounds toward ethylene polymerization has been investigated. / Chapter 5 describes the development of group 4 metal complexes from 1-azaallyls. Lithium cyclohexenyl-1-azaallyl compound [(TMEDA)LiN(SiMe3)C(Ph)= CHCHC&parl0;SiMe3&parr0;CH2CH 2C H2] (149) and zirconium(IV) dichloride compound [Zr{N(SiMe3)C(Ph)(L)}2Cl2] (L = CHCHC&parl0;SiMe3&parr0;CH2CH 2C H2) (150) were synthesized. Novel anionic one-dimensional bifunctional lithium compound [{(THF)Li(N(SiMe3))2C}(CN)C 6H4-1,4)]n (151) has also been synthesized. Similar reactions of 1,2-dicyanobenzene, 1,3-dicyanobenzene or 1,4-dicyanobenzene with lithium amide [(Et2O)2LiN(SiMe3) 2] afforded lithium bis(1,3-diazaallyl) compounds [{(THF)2Li(N(SiMe 3))2C}C6H4-1,2)] (152), [{(THF)2Li(N(SiMe3))2C}C6H 4-1,3)] (153) and [{(THF)2Li(N(SiMe3)) 2C}C6H4-1,4)] (154), respectively. / The work presented in this thesis is mainly focused in two parts: (i) the synthesis and reactivities of low-valent main group 14 metal complexes derived from phosphoranoimines, (ii) the synthesis and catalytic studies of transition group 4 metal complexes derived from phosphoranoimines and 1-azaallyl ligands. / Wong Kam Wing. / "December 2006." / Adviser: Kevin Wing-Por Leung. / Source: Dissertation Abstracts International, Volume: 68-08, Section: B, page: 5233. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references. / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [200-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstracts in English and Chinese. / School code: 1307.
| Identifer | oai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_343814 |
| Date | January 2006 |
| Contributors | Wong, Kam Wing., Chinese University of Hong Kong Graduate School. Division of Chemistry. |
| Source Sets | The Chinese University of Hong Kong |
| Language | English, Chinese |
| Detected Language | English |
| Type | Text, theses |
| Format | electronic resource, microform, microfiche, 1 online resource (xvi, 199 p. : ill.) |
| Rights | Use of this resource is governed by the terms and conditions of the Creative Commons “Attribution-NonCommercial-NoDerivatives 4.0 International” License (http://creativecommons.org/licenses/by-nc-nd/4.0/) |
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