Transition-metal derivatives of phosphine, arsine and stibine
This thesis describes the synthesis of complexes of Iridium containing PH2, PH3, AsH2 and SbH2 ligands, prepared by the reaction of MH3(M = P, As, Sb) with Ir(CO)X(PEt3)2 (X = Cl, Br). The crystal structure of Ir(CO)HC1(PEt3)2AsH2 is reported. The reactions of these complexes with oxidants and Lewis...
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| Format: | Dissertation |
| Language: | English |
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ProQuest Dissertations & Theses
01-01-1986
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| Online Access: | Get full text |
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| Summary: | This thesis describes the synthesis of complexes of Iridium containing PH2, PH3, AsH2 and SbH2 ligands, prepared by the reaction of MH3(M = P, As, Sb) with Ir(CO)X(PEt3)2 (X = Cl, Br). The crystal structure of Ir(CO)HC1(PEt3)2AsH2 is reported. The reactions of these complexes with oxidants and Lewis acids and bases are described. Facile interconversion between PH2 and PH3 groups is achieved by using HC1 or Me3N, but stable complexes of AsH3 were not observed. Complexes containing terminal PH2 and AsH2 groups were used in the controlled synthesis of mixed-metal bridging phosphido complexes. The X-ray crystal structures of two of these species (Ir(CO)HBr(PEt3)2( 2PH2)RuCl2p-Cymene) and Ir(CO)HC1(PEt3)2( 2AsH2)RuCl2(p-Cymene)) are reported. Complexes containing two metal centres and two PH2 groups in a four-membered ring arrangement were prepared by the reaction of the bidentate bis -PH2 complex Ir(CO)H(PEt3)2(PH2)2 with appropriate transition-metal substrates. The n.m.r. parameters of all these species are tabulated and commented upon. Attempts to generate complexes containing phosphorus in unusual modes are described, and species containing phosphorus-phosphorus triple bonds and phosphorus-metal double bonds are postulated. Reactions of Ir(CO)Cl2(PEt3)2PCa2 with a range of covalent and ionic hydrides are discussed, and the n.m.r. parameters of the products reported and analysed. Some results of the reactions of Rh(CO)Cl(PEt3)2 with PH3, PH3BC1 and BC13 are presented. (D73870/87) |
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