ABSTRACT Recently developed our systematic syntheses of homo- and heterotrimetallic platinum clusters through diplatinum precursors with tridentate phosphine ligand, bis(diphenylphosphinomethyl)phenylphosphine (dpmp), are reviewed in this paper. Reaction of [Pt2(RNC)6] 2+ (RNC = aromatic isocyanide) with dpmp afforded an isomeric mixture of syn- and anti-[Pt2(μ-dpmp)2- (RNC)2]2+ (1 and 2). The differential reactivity of 1 (syn) and 2 (anti) allows an access to versatile aggregations of homo and hetero trinuclear clusters. The former was transformed by treatment with d10 pt0,Pd0, AuI, AgI, and CuI and d8 PtII, PdII, Irl, and RhI species to a wide variety of Pt-Pt-M clusters. Treatment of complex 2 with Pt0 and Pd0 fragments gave Pt-M-Pt A-frame clusters (M = Pt, Pd). The inserted position of the additional metal is interestingly depends on the two dpmp arrangement of the starting diplatinum complexes. The corresponding chemistry of palladium clusters is also described.
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