Reactions of Cp(CO)2Re=C=CHPh with Pt[P(OR)3]4 (R = Pri, Et, Ph) gave binuclear μ-vinylidene complexes Cp(CO)2RePt(µ-C=CHPh)[P(OR)3]2. Treatment of the previously synthesized Cp(CO)2Re(µ-C=CHPh)Pt(PPh3)2 with triisopropylphosphite or triethylphosphite resulted in a stepwise substitution of PPh3 ligands, leading to the disubstituted Cp(CO)2RePt(µ-C=CHPh)[P(OR)3]2 and monosubstituted Cp(CO)2RePt(µ-C=CHPh)[