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[摘要]：Reactions of SnCl(2) with the complexes cis-[PtCl(2)(P(2))](P(2) = dppf (1,1'-bis(diphenylphosphino)ferrocene), dppp (1,3-bis(diphenylphosphino)propane = 1,1'-(propane-1,3-diyl)bis[1,1-diphenylphosphine]), dppb (1,4-bis(diphenylphosphino)butane = 1,1'-(butane-1,4-diyl)bis[1,1-diphenylphosphine]), and dpppe (1,5-bis(diphenylphosphino)pentane = 1,1'-(pentane-1,5-diyl)bis[1,1-diphenylphosphine])) resulted in the insertion of SnCl(2) into the Pt-Cl bond to afford the cis-[PtCl(SnCl(3))(P(2))] complexes. However, the reaction of the complexes cis-[PtCl(2)(P(2))](P(2) = dppf, dppm (bis(diphenylphosphino)methane = 1,1'-methylenebis[1,1-diphenylphosphine]), dppe(1,2-bis(diphenylphosphino)ethane = 1,1'-(ethane-1,2-diyl)bis[1,1-diphenylphosphine]), dppp, dppb, and dpppe; P = Ph(3)P and(MeO)(3)P) with SnX(2) (X = Br or I) resulted in the halogen exchange to yield the complexes [PtX(2)(P(2))]. In contrast, treatment of cis-[PtBr(2)(dppm)] with SnBr(2) resulted in the insertion of SnBr(2) into the Pt-Br bond to form cis-[Pt(SnBr(3))(2)(dppm)], and this product was in equilibrium with the starting complex cis-[PtBr(2)(dppm)]. Moreover, the reaction of cis-[PtCl(2)(dppb)] with a mixture SnCl(2)/SnI(2) in a 2 : 1 mol ratio resulted in the formation of cis-[PtI(2)(dppb)] as a consequence of the selective halogen-exchange reaction. (31)P-NMR Data for all complexes are reported, and a correlation between the chemical shifts and the coupling constants was established for mono- and bis(trichlorostannyl)platinum complexes. The effect of the alkane chain length of the ligand and Sn(II) halide is described. |
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