Chapter 1 describes the reactivities of bisgermavinylidene [(Me 3SiN=RPh2)2C=Ge→Ge=C(PPh2=NSiMe 3)2] (25). With the use of CpMnCO2(THF), Mn2(CO)10 and group 11 metal halides, manganese-germavinylidene complexes and germavinylidyl group 11 metal complexes were prepared respectively. Radical reaction of 25 with 2,2,6,6-tetramethylpiperidine N-oxide affords [(Me3SiN=RPh2)2C=Ge(ONCMe2C 3H6CMe2)2] (40). Cycloadditon reactions of 25 were studied. The reaction of 25 with benzil, azobenzene or 3,5-di-tert-butyl-o-benzoquinone affords [(Me3SiN=PPh2)2C=Ge{O(Ph)C=C(Ph)O}] (41), [(Me3SiN=PPh2)2C=Ge( o-C6H4NHNPh)](42) and [(Me 3SiN=PPh2)2C=Ge=C-(PPh2=NSiMe 3)2] (44), respectively. The C=Ge bond of 25 can undergo cycloaddition reactions with Me3SiN 3, Me3SiCHN2 or AdNCO (Ad = adamantly) to give [(Me3SiN=PPh2)2CGeN(SiMe3)N=N] (46), [(Me3SiN=PPh2)2C-GeN=NCH-SiMe 3] (48) and [(Me3SiN=PPh2)2 CGeN(Ad)C-O] (47), respectively. Furthermore, 1,2-addition products of rhodium(I) and tin(IV) complexes were prepared from the reaction of 25 with (cod)RhCl and (nBu) 3SnN3, respectively. The syntheses of bimetallic chlorides [(Me3SiN=PPh2)2(GcCl)CMn(mu-Cl)]2 (51) and [(Me3SiN=PPh2)2(GeCl)CFeCl] (52) are also reported. / Chapter 2 concerns the reactivities of bis(iminophosphorano)methanide tin(II) chloride [HC(PPh2=NSiMe3)2SnCl] ( 79). The reactivity of the lone pair in 79 was studied. The reaction of 79 with benzil or 3,5-di-tert-butyl- o-benzoquinone gives the corresponding cycloaddition products. Treatment of 79 with NaN3 or AgOSO2CF3 affords the corresponding substituted heteroleptic stannylenes. The reaction of 79 with W(CO)5THF gives an adduct [HC(PPh 2=NSiMe3)2(Cl)Sn→W(CO)5] ( 81). Compound 79 reacts with Fe{N(SiMe3) 2}2 to afford [HC(PPh2=NSiMe3) 2Fe(mu-Cl)]2 (86). Moreover, treatment of 79 with LiC≡CPh gives [HC(PPh2=NSiMe3) 2C(Sn)=C(Ph)Sn(C≡CPh)2]2 (87). / Chapter 3 deals with the preparation and characterization of group 14 bis(thiophosphinoyl) metal complexes. The newly developed ligand [(S=PPr i2CH2)2-C5H 3N-2,6] (126) undergoes metalation with nBuLi or (nBu)2Mg to afford the lithium complex [Li{(S=PPri 2CH)(S=PPi2CH2)C 5H3N-2,6}(Et2O)] (127) and magnesium complex [Mg(S=PPri2CH)2C 5H3N-2,6] (128), respectively. 1,3-Distannylcyclobutane and 1,3-diplumbacyclobutane were prepared from treatment of 126 with M{N(SiMe3)2}2 (M Sn, Pb) by the amine-elimination reaction. Furthermore, compound 127 reacts with GeCl2.dioxane or SnCl2 to afford digermylgermylene Ge[GeCl2{(S=PPr i2CH)(S=PPri 2CH2)C5H3N-2,6}]2 ( 131) and ionic tin(II) complex [{C5H3N-2,6-(CH 2PPri2=S)(CHPPr i2=S)}SN+][SnCl3 -] (134), respectively. / Chapter 4 describes the conclusion of the first three chapters. The future works of the first three chapters were also reported. / This thesis is focused on four areas: (i) the reactivities of bisgermavinylidene; (ii) the reactivities of bis(iminophosphorano)methanide tin(II) chloride; (iii) the synthesis of group 14 bis(thiophosphinoyl) metal complexes and (iv) conclusions and future works. / Kan, Kwok Wai. / "Aug 2007." / Adviser: Kevin W. P. Leung. / Source: Dissertation Abstracts International, Volume: 69-02, Section: B, page: 1007. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2007. / 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. / Abstract in English and Chinese. / School code: 1307.
| Identifer | oai:union.ndltd.org:cuhk.edu.hk/oai:cuhk-dr:cuhk_344078 |
| Date | January 2007 |
| Contributors | Kan, Kwok Wai., 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, 211 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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