SCHEDULED MAINTENANCE
Preparation of compounds containing platinum–silicon bonds from silicon hydrides and platinum(0) complexes
Abstract
The complexes [Pt(SiCl3)2(PPh3)2], [Pt(SiCl3)2(diphos)](diphos = Ph2PCH2CH2PPh2), [Pt(SiHPh2)2(diphos)], and [PtH{Si(C6H4X)3}(PPh3)2](X =m- and p-F or -CF3) have been prepared by treatment of the complex [Pt(PPh3)4] or [Pt(diphos)2] with the silicon hydride Cl3SiH, Ph2SiH2, or (XC6H4)3SiH. All probably have cis-configurations.
The complex [Pt(SiHPh)2(diphos)] reacts with 1 molar proportion of bromine to give [Pt(SiBrPh2)2(diphos)], in a reaction representing the first substitution at silicon attached to platinum without cleavage of the Pt–Si bond. (With 2 molar proportions of bromine, cleavage does occur, to give the complex [PtBr2(diphos)].) In another such reaction, the silyl bromide [Pt(SiBrPh2)2(diphos)] reacts with methyl-lithium to give the complex [Pt(SiMePh2)2(diphos)].
Silyl–ligand exchange occurs when [PtH{Si(C6H4X)3}(PPh3)2] or [Pt(SiMePh2)2(PMe2Ph)2] is treated with an excess of trichlorosilane, the product being [Pt(SiCl3)2(PPh3)2] or [Pt(SiCl3)2(PMe2Ph)2], respectively.
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