DIMETHYL SULFIDE SUBSTITUTED MIXED-METAL CLUSTERS - SYNTHESIS, STRUCTURE, AND CHARACTERIZATION OF HRUCO3(CO)11(SME2) AND [HRURH3(CO)9]2[SME2]3

Ligand substitution reactions of dimethyl sulfide with mixed-metal clusters are described. The clusters HRuCo3(CO)11(SMe2) (1) and [HRuRh3(CO)9]2[SMe2]3 (2) have been prepared by reactions of SMe2 with the neutral parent clusters. Their crystal structures have been established: 1, monoclinic, space group P21/n, a = 11.459 (5) Å, b = 12.484 (4) Å, c = 14.384 (4) Å, β = 96.40 (3)°, Z = 4; 2, trigonal, space group R3c, a = 13.181 (7) Å, α = 75.54 (5)°, Z = 2. Dimethyl sulfide coordinates terminally as a two-electron donor on basal cobalt in 1 and as a bridging four-electron donor causing unusual dimerization of clusters in 2. The carbonyl arrangement of the parent clusters was not changed during the ligand substitution, and hydride ligands bridge the three basal metals in both compounds. © 1990, American Chemical Society. All rights reserved.