Electrochemical reduction of cis-[PtCl2(PR3)2] (R = Ph, Et) in CH3CN/C6H6 containing NBu4C104 at a Hg pool electrode generates [Pt(PR3)2] equivalents in solution. Where R = Ph, the [Pt(PR3)2] equivalent may be trapped by 02, 02/C02, HC1, Mel, C6H6C0C1, and RC=CR (R = Ph, COOMe) but not by the less -reactive substrate PhCl. Where R = Et, the [Pt(PR3)2] equivalent reacts with the NBu4+ cation to ultimately generate trans-[PtH(Cl)(PEt3)2]. Prolonged electrolyses cause reduction of trans-[PtH(Cl) (PEt3)2] leading to hydride attack on the CH3CN solvent and ultimately forming trons-[PtH(CH2CN) (PEt3)2]. In the presence of bases such as NBu3, trans-[PtH(CH2CN) (PEt3)2] is isomerized in CH3CN solution producing iruns-[PtCN(CH3) (PEt3)2]. The use of electroinactive trapping agents such as PhCl or PhCN as cosolvents for the reduction of cis-[PtCl2(PEt3)2] allows trapping of the [Pt(PEt3)2] equivalents as irons-[PtPh-(X)(PEt3)2] (X = Cl, CN).

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