The cyclometalated platinum complex [PtMe(bhq)(dppy)] (1), in which bhq = benzo h)quinoline and c1ppy = 2-(diphenylphosphino)pyridine, was prepared by the reaction of [PtMe(SMe2)(bhq)] with 1 equiv of dppy at room temperature. Complex 1 contains one free pyridyl unit and was readily characterized by multinuclear NMR spectroscopy and elemental microanalysis. The reaction of complex 1 with 1 equiv of [Ag(CH3CN)4]BF4 gave the cyclornetalated cluster complex [Pt2Me2(bhq)(2)(mu-dPPY)(2)Ag-2(mu-acetone)](BF4)(2) (2) in 70% yield. The crystal structure of complex 2 was determined by X-ray crystallography, indicating a rare example of a butterfly cluster with a Pt2Ag2 core in which the Ag atoms occupy the edge-sharing bond, In solution, the bridging acetone dissociates from the cluster complex 2, but as shown by NMR spectroscopy, the Pt2Ag2 core is retained in solution and a dynamic equilibrium is suggested to be established between the planar and butterfly skeletal geometries.