Mixed-metal sulfido clusters containing noble metals and group 15 metals. Stepwise construction of bimetallic and trimetallic Ru2MS2 (M = Sb, Bi), Ru2PdSbS2, and Ru2Pd2SbS2 cores

摘要

By starting from a diruthenium bis(mu-hydrosulfido) complex [((CpRuCl)-Ru-o)(2)(mu-SH)(2)] (1; Cp-o = eta(5)-C5Me4Et), a series of new mixed-metal sulfur clusters containing both noble metals and group 15 metals have been synthesized. Thus, 1 was allowed to react with 1 equiv of MCl3 (M = Sb, Bi) to give the trinuclear Ru2M clusters [((CpRuCl)-Ru-o)(2)(mu-SMCl2)(mu-SH)] (3a, M = Sb; 3b, M = Bi) containing bridging SH and SMCl2 ligands. Treatment of 3a with 1 equiv of [Pd(PPh3)(4)] at room temperature gave a mixture of the Ru-Pd-Sb clusters [((CpRu)-Ru-o)((CpRuCl)-Ru-o)(mu-SSbCl2){PdCl(PPh3)}(mu(3)-S)(mu-H)] (4), [((CpRu)-Ru-o)(2)(SbCl2){Pd(PPh3)}(2)(mu(3)-S)(2)(mu-Cl)] ( 5), and [((CpRu)-Ru-o)((CpRuCl)-Ru-o){PdCl(PPh3)}(SbCl)(mu(3)-S)(2)] (6). An analogous reaction carried out at -5 degrees C gave 4 as the major product. By contrast, isolation of the Bi analogues from the reaction of 3b and [Pd(PPh3)(4)] was unsuccessful. It was also confirmed that the isolated 4 was treated with 1 equiv of [Pd(PPh3)(4)] in THF either at 50 degrees C or at room temperature in the presence of triethylamine to give 5, while 4 was converted to 6 upon either warming to 50 degrees C or dehydrochlorination by the use of triethylamine in THF. Cluster 6 was readily transformed into 5 by treatment with [Pd(PPh3)(4)] in THF at room temperature. Structures of the new clusters 3a, 3b, 4, 5, and 6 have been determined by single-crystal X-ray analysis.