Isocyanide complexes of platinum(0)

Abstract

Treatment of [Pt(C₂H₄)(PPh₃)₂] with t-butyl isocyanide yields the complex [Pt(CNBu^t)₂(PPh₃)₂], and evidence for the existence of related species [Pt(CNR)₂(PPh₃)₂](R = Prⁱ, C₆H₁₁, p-MeOC₆H₄, or p-ClC₆H₄) has been obtained from solution studies. Displacement of the arsine ligand from [Pt(AsPh₃)₂(C₂F₄)] with RNC (R = Prⁱ or Bu^t) yields the complexes [Pt(CNR)₂(C₂F₄)]. Oxidative-addition reactions of [Pt(CNBu^t)₂(PPh₃)₂] occur with I₂, Mel, CF₃I, and [SnPh₃Cl], the products being best formulated as [Pt(CNBu^t)₂(PPh₃)₂I]I or [Pt(CNBu^t)(CR = NBu^t)(PPh₃)₂]I except for the adduct with [SnPh₃Cl]. Alternative routes to some of the products have been found, such as the interaction of [PtMe(I)(PPh₃)₂] with Bu^tNC. An unusual reaction occurs on attempted alkylation of the cyanide [Pt(CN)₂(PPh₃)₂] with Mel in that the phosphine ligands are displaced and [Pt(CNMe)₂I₂] is obtained.