Reactions of the tungsten tris-sulfido complex [PPh 4][( η5-C 5Me 5)WS 3] with [M′(PPh 3) 2(NO 3)] (M′=Cu(I), Ag(I)), [Au(PPh 3)Cl], and [Pd(dppe)Cl 2]: Isolation and structures of [( η5-C 5Me 5)WS 3Cu 3(PPh 3) 3(NO 3)][NO 3], [{( η5-C 5Me 5)WS 3} 2Ag 3(PPh 3) 3][NO 3], [( η5-C 5Me 5)WS 3Au(PPh 3)] and [( η5-C 5Me 5)WS 3Pd(dppe)]Cl

Abstract

The reactions of [PPh 4][( η 5-C 5Me 5)WS 3] with [M′(PPh 3) 2(NO 3)] (M′=Cu(I) or Ag(I)), [Au(PPh 3)Cl], and [Pd(dppe)Cl 2] (dppe=1,2-bis(diphenylphosphino)ethane) in CH 3CN yielded four new heterobimetallic clusters in good yields: [( η 5-C 5Me 5)WS 3Cu 3(PPh 3) 3(NO 3)][NO 3] ( 1), [{( η 5-C 5Me 5)WS 3} 2Ag 3(PPh 3) 3][NO 3] ( 2), [( η 5-C 5Me 5)WS 3Au(PPh 3)] ( 3), and [( η 5-C 5Me 5)WS 3Pd(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 3Cu 3 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, [( η 5-C 5Me 5)WS 3Ag 2(PPh 3) 2] + and [( η 5-C 5Me 5)WS 3Ag(PPh 3)], which are linked by Ag–S interactions. In the structures of 3 and 4, Au(PPh 3) and Pd(dppe) fragments bridge two sulfur atoms of the common ( η 5-C 5Me 5)WS 3 fragment, respectively. The behavior of 1–4 in solution was examined by ESI–MS.