Dppm-substituted ruthenium clusters with capping sulfido and selenido ligands derived from thiourea, tetramethylthiourea and elemental selenium

Abstract

Treatment of [Ru 3(CO) 10(μ-dppm)] ( 4) [dppm = bis(diphenylphosphido)methane] with tetramethylthiourea at 66 °C gave the previously reported dihydrido triruthenium cluster [Ru 3(μ-H) 2(μ 3-S)(CO) 7(μ-dppm)] ( 5) and the new compounds [Ru 3(μ 3-S) 2(CO) 7(μ-dppm)] ( 6), [Ru 3(μ 3-S)(CO) 7(μ 3-CO)(μ-dppm)] ( 7) and [Ru 3(μ 3-S){η 1-C(NMe 2) 2}(CO) 6(μ 3-CO)(μ-dppm)] ( 8) in 6%, 10%, 32% and 9% yields, respectively. Treatment of 4 with thiourea at the same temperature gave 5 and 7 in 30% and 10% yields, respectively. Compound 7 reacts further with tetramethylthiourea at 66 °C to yield 6 (30%) and a new compound [Ru 3(μ 3-S) 2{η 1-C(NMe 2) 2}(CO) 6(μ-dppm)] ( 9) (8%). Thermolysis of 8 in refluxing THF yields 7 in 55% yield. The reaction of 4 with selenium at 66 °C yields the new compounds [Ru 3(μ 3-Se)(CO) 7(μ 3-CO)(μ-dppm)] ( 10) and [Ru 3(μ 3-Se)(μ 3-η 3-PhPCH 2PPh(C 6H 4)}(CO) 6(μ-CO)] ( 11) and the known compounds [Ru 3(μ-H) 2(μ 3-Se)(CO) 7(μ-dppm)] ( 12) and [Ru 4(μ 3-Se) 4(CO) 10(μ-dppm)] ( 13) in 29%, 5%, 2% and 5% yields, respectively. Treatment of 10 with tetramethylthiourea at 66 °C gives the mixed sulfur-selenium compounds [Ru 3(μ 3-S)(μ 3-Se)(CO) 7(μ-dppm)] ( 14) and [Ru 3(μ 3-S)(μ 3-Se){η 1-C(NMe 2) 2}(CO) 6(μ-dppm)] ( 15) in 38% and 10% yields, respectively. The single-crystal XRD structures of 6, 7, 8, 10, 14 and 15 are reported.