Triosmium and triruthenium clusters containing the 4-methylthiazolide ligand: crystal structures of [Os3(µ-H)(CO)10(µ-2,3-η2-CNCMeCHS)], [Os3(µ-H)(CO)9(µ-2,3-η2-CNCMeCHS)(PPh3)] and [Os3(µ-H)(CO)8(µ-2,3-η2-CNCMeCHS)(PPh3)2]

Abstract

The reaction of [Os₃(CO)₁₀(MeCN)₂] with 4-methylthiazole at room temperature gave [Os₃(µ-H)(CO)₁₀(µ-2,3-η²-[graphic omitted])]1, in which the thiazolide ligand is co-ordinated to the cluster through the nitrogen and carbon atoms of the CN bond, in high yield. Compound 1 reacted with PPh₃ at 110 °C to give [Os₃(µ-H)(CO)₉(µ-2,3-η²-[graphic omitted])(PPh₃)]2 and [Os₃(µ-H)(CO)₈(µ-2,3-η²-[graphic omitted])(PPh₃)₂]3. Compound 2 exists as two isomers in solution whereas 3 exists as four. The reaction of 2 with PPh₃ at 110 °C yielded 3 in good yield. Compound 1 reacted with 4-methylthiazole at 110 °C to give [Os₃(µ-H)₂(CO)₈(µ-2,3-η²-[graphic omitted])(µ-1,5-η²-[graphic omitted])]4 and [Os₃(µ-H)₂(CO)₈(µ-2,3-η²-[graphic omitted])₂]5. In 4 the second thiazolide ligand is co-ordinated through the sulfur and C(5) carbon atoms whereas in 5 both ligands are co-ordinated through the nitrogen and C(2) carbon atoms. The reaction of [Ru₃(CO)₁₂] with 1 equivalent of 4-methylthiazole in the presence of sodium–benzophenone at 67 °C gave [Ru₃(µ-H)(CO)₁₀(µ-2,3-η²-[graphic omitted])]6 whereas with 2 equivalents it gave [Ru₃(µ-H)₂(CO)₈(µ-2,3-η²-[graphic omitted])₂]7. Compounds 6 and 7 are the structural analogues of 1 and 4 respectively. The reaction of 6 with 1 equivalent of 4-methylthiazole in the presence of sodium–benzophenone gave 7. All the compounds were characterized by ¹H NMR and infrared spectroscopy and elemental analysis. In addition, the solid-state structures for 1–3 were determined.