Reactivity of Heterodinuclear Complexes Formed by Platinum Insertion to Phosphorus-Bridged [1]Ferrocenophane Coordinating to a Metal Fragment
作者:Tsutomu Mizuta、Makoto Onishi、Tohru Nakazono、Hiroshi Nakazawa、Katsuhiko Miyoshi
DOI:10.1021/om010797i
日期:2002.2.1
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 eta(1)-C5H4-Pt bonds with a mu-PPhFc bridge (mu-PPhFc = mu-PPh(C5H4FeC5H4)). X-ray analyses showed that the products were Cp(CO)(2)Mn(mu-PPhFc)Pt(PMe3)(2) and (CO)(5)W(mu-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(mu-CO)(mu-PPhFc)Pt(PPh3), whereas W(CO)(5)(fcpp) gave (CO)(4)W(mu-PPh2)(mu-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)(5)W(mu-PPhFc)Pt(CO)(PPh3), cis-W- and trans-W-(CO)(4)(PPh3)W(mu-PPhFc)Pt(CO)(PPh3), and cis-W-(CO)(4)(PPh3)W(mu-CO)-(mu-PPhFc)Pt(PPh3).