Reaction of Ketenylidenetriphenylphosphorane (Ph₃PCCO) with Platinum(II) and Palladium(II) Complexes. Synthesis, Characterization, and Molecular Structure of [Pt(η³-C₃H₅){η¹-C(PPh₃)(CO)}(PPh₃)]BF₄

Abstract

Ketenylidenetriphenylphosphorane, Ph3P CCO, reacts with Pt(II) and Pd(II) η3-allyl complexes (allyl = C3H5, 2-MeC3H4) to give neutral or cationic mononuclear η1-ketenyl derivatives [M(η3-allyl){(η1-C(PPh3)(CO)}L]m+ (L = Cl, m = 0; L = PPh3, m = 1) that have been characterized by elemental analysis, IR, and multinuclear NMR. The X-ray molecular structure determination performed on a single crystal of the air-stable derivative [Pt(η3-C3H5){η1-C(PPh3)(CO)}(PPh3)]BF4 furnishes the first crystallographic evidence of an η1-ketenyl derivative in which the ketene moiety is also involved in an ylide grouping.