Reactivity of Heterodinuclear Complexes Formed by Platinum Insertion to Phosphorus-Bridged [1]Ferrocenophane Coordinating to a Metal Fragment

A reaction of Pt(PMe 3 ) 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(PMe 3 ) 2 fragment was inserted into a P−C bond of the fcpp ligand to form P−Pt and η 1 -C 5 H 4 −Pt bonds with a μ-PPhFc bridge (μ-PPhFc = μ-PPh(C 5 H 4 FeC 5 H 4 )). X-ray analyses showed that the products were Cp(CO) 2 Mn(μ-PPhFc)Pt(PMe 3 ) 2 and (CO) 5 W(μ-PPhFc)Pt(PMe 3 ) 2, respectively. Upon a similar reaction employing Pt(PPh 3 ) 4 in place of Pt(PMe 3 ) 4, CpMn(CO) 2 (fcpp) gave Cp(CO)Mn(μ-CO)(μ-PPhFc)Pt(PPh 3 ), whereas W(CO) 5 (fcpp) gave (CO) 4 W(μ-PPh 2 )(μ-PPh(C 5 H 4 FeC 5 H 4 Ph))Pt(PPh 3 ), in which cleavage of a P−Ph bond of PPh 3 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) 5 W(μ-PPhFc)Pt(CO)(PPh 3 ), ci s- W - and trans - W -(CO) 4 (PPh 3 )W(μ-PPhFc)Pt(CO)(PPh 3 ), and cis - W -(CO) 4 (PPh 3 )W(μ-CO)(μ-PPhFc)Pt(PPh 3 ).