AbstractThe dinuclear complex [(C6F5)2Pt(μ‐PPh2)2Pt(NCCH3)2] (1) is described and fully characterised. Complex 1 reacts with 2,2′‐bipyrimidine and cis‐[M(C6F5)2(THF)2] to form the di‐, tri‐ and tetranuclear complexes 2, 3 and 4, respectively, depending on the ratio of reagents and the type of metal (M = Pt, Pd). Complex 1 reacts with KCN to form the anionic dinuclear complex [PPh3(CH3)]2[(C6F5)2Pt(μ‐PPh2)2Pt(CN)2] (6). Complex 6 acts as a metalloligand towards cis‐[M(C6F5)2(THF)2] or 1 to yield the corresponding hexanuclear or octanuclear complexes 7, 8 and 9. The structure of [PPh3(CH3)]4[{(C6F5)2Pt(μ‐PPh2)2Pt(μ‐CN)2Pd(C6F5)2}2] (8) has been established by X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)