PREPARATION OF DIPHENYLPHOSPHIDO-BRIDGED AND PHENYLTHIO-BRIDGED DINUCLEAR PLATINUM(II) COMPLEXES BY USE OF "TRIMETHYL(DIPHENYLPHOSPHINO)-SILANE AND TRIMETHYL(PHENYLTHIO)-SILANE

The complexes [Pt2Cl2(μ-Cl)2L2] (L = triorganophosphine) react with 2 molar proportions of SiMe3(PPh2) in tetrahydrofuran or CH2Cl2 at room temperature to give the corresponding phosphido-bridged complexes trans-[Pt2Cl2(μ-PPh2)2L2]. The same products are formed, in lower yield, by treatment of cis-[PtCl2L2] complexes with 1 molar proportion of SiMe3(PPh2), and the arsine complex trans-[Pt2Cl2(μ-PPh2)2(AsEt3)2] is produced analogously from cis-[PtCl2(AsEt3)2]. The corresponding reaction with trans-[Pt(Cl)H(PEt3)2] gives trans-[Pt2H2(μ-PPh2)2(PEt3)2]. Treatment of trans-[Pt2Cl2(μ-Cl)2L2] complexes with SiMe3(SPh) gives cis-[Pt2Cl2(μ-Cl)(μ-SPh)L2], trans-[Pt2Cl2(μ-SPh)2L2], or trans-[Pt2(SPh)2(μ-SPh)2L2] depending upon the molar proportion of SiMe3(SPh) and the temperature used, while cis-[PtCl2L2] gives trans-[Pt(SPh)2L2]. Ethylation of trans-[PtCl2(μ-SPh2)L2] (L = P-n-Pr3) with [OEt3]BF4 appears to give the chloride-bridged trans-[Pt2(μ-Cl)2(SEtPh)2L2][BF4]2. © 1979.