Reactions of the tungsten tris-sulfido complex [PPh4][(η5-C5Me5)WS3] with [M′(PPh3)2(NO3)] (M′ = Cu(I), Ag(I)), [Au(PPh3)Cl], and [Pd(dppe)Cl2]:: Isolation and structures of [(η5-C5Me5)WS3Cu3(PPh3)3(NO3)][NO3], [{(η5-C5Me5)WS3}2Ag3(PPh3)3][NO3], [(η5-C5Me5)WS3Au(PPh3)] and [(η5-C5Me5)WS3Pd(dppe)]Cl (dppe = 1,2-bis(diphenylphosphino)ethane)

The reactions of [PPh4][(eta(5)-C5Me5)WS3] with [M'(PPh3)(2)(NO3)] (M' = Cu(I) or Ag(I)), [Au(PPh3)Cl], and [Pd(dppe)Cl-2] (dppe= 1,2-bis(diphenylphosphino)ethane) in CH3CN yielded four new heterobimetallic clusters in good yields: [(eta(5)C(5)Me(5))WS3Cu3(PPh3)(3)(NO3)][NO3] (1), [{(eta(5)-C5Me5)WS3}(2)Ag-3(PPh3)(3)][NO3] (2), [(eta(5)-C5Me5)WS3Au(PPh3)] (3), and [(eta(5)-C5Me5)WS3Pd(dppe)]Cl (4). Analytically pure compounds 1-4 were characterized by spectroscopy and their crystal structures were determined by single-crystal X-ray analysis. The structure of the cation of 1 has an incomplete WS,Cu, cube, and one nitrate group interacts strongly with one copper atom. The structure of the cation of 2 may be viewed as a composite of the two subcluster units, [(eta(5)-C5Me5)WS3Ag2(PPh3)(2)](+) and [(eta(5)-C5Me5)WS3Ag(Phh(3))], which are linked by Ag-S interactions. In the structures of 3 and 4, Au(PPh3) and Pd(dppe) fragments bridge two sulfur atoms of the common (eta(5)-C5Me5)WS3 fragment, respectively. The behavior of 1-4 in solution was examined by ESI-MS. (C) 1998 Elsevier Science S.A. All rights reserved.