A reaction of Pt(PMe3)4 with fcpp (fcpp = 1,1‘-ferrocenediylphenylphosphine) coordinating to CpMn(CO)2 and W(CO)5 fragments gave heterodinuclear complexes (actually they are trinuclear complexes if an iron center of a ferrocene unit is included), in which a Pt(PMe3)2 fragment was inserted into a P−C bond of the fcpp ligand to form P−Pt and η1-C5H4−Pt bonds with a μ-PPhFc bridge (μ-PPhFc = μ-PPh(C5H4FeC5H4)). X-ray analyses showed that the products were Cp(CO)2Mn(μ-PPhFc)Pt(PMe3)2 and (CO)5W(μ-PPhFc)Pt(PMe3)2, respectively. Upon a similar reaction employing Pt(PPh3)4 in place of Pt(PMe3)4, CpMn(CO)2(fcpp) gave Cp(CO)Mn(μ-CO)(μ-PPhFc)Pt(PPh3), whereas W(CO)5(fcpp) gave (CO)4W(μ-PPh2)(μ-PPh(C5H4FeC5H4Ph))Pt(PPh3), in which cleavage of a P−Ph bond of PPh3 and migration of the Ph group to a ferrocene moiety took place. To elucidate the reaction mechanism, several reaction intermediates were isolated and characterized as (CO)5W(μ-PPhFc)Pt(CO)(PPh3), cis-W- and trans-W-(CO)4(PPh3)W(μ-PPhFc)Pt(CO)(PPh3), and cis-W-(CO)4(PPh3)W(μ-CO)(μ-PPhFc)Pt(PPh3).

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