Triosmium and triruthenium clusters containing the 4-methylthiazolide ligand: Crystal structures of [Os-3(mu-H)(CO)(10)(mu-2,3-eta(2)-C=NCMe-CHS)], [Os-3(mu-H)(CO)(9)(mu-2,3-eta(2)-C=NCMe=CHS)(PPh(3))] and [Os-3(mu-H)(CO)(8)(mu-2,3-eta(2)-C=NCMe=CHS)(PPh(3))(2)]

The reaction of [Os-3(CO)(10)(MeCN)(2)] with 4-methylthiazole at room temperature gave [Os-3(mu-H)(CO)(10)-(mu-2,3-eta(2)-C=NCMe=CHS)] 1, in which the thiazolide ligand is co-ordinated to the cluster through the nitrogen and carbon atoms of the C=N bond, in high yield. Compound 1 reacted with PPh(3) at 110 degrees C to give [Os-3(mu-H)(CO)(9)(mu-2,3-eta(2)-C=NCMe=CHS)(PPh(3))] 2 and [Os-3(mu-H)(CO)(8)(mu-2,3-eta(2)-C=NCMe=CHS)(PPh(3))(2)] 3. Compound 2 exists as two isomers in solution whereas 3 exists as four. The reaction of 2 with PPh(3) at 110 degrees C yielded 3 in good yield. Compound 1 reacted with 4-methylthiazole at 110 degrees C to give [Os-3(mu-H)(2)(CO)(8)(mu-2,3-eta(2)-C=NCMe=CHS)(mu-1,5-eta(2)-CH=NCMe=CS)] 4 and [Os-3(mu-H)(2)(CO)(8)(mu-2,3-eta(2)-C=NCMe=CHS)(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 [Ru-3(CO)(12)] with 1 equivalent of 4-methylthiazole in the presence of sodium-benzophenone at 67 degrees C gave [Ru-3(mu-H)(CO)(10)(mu-2,3-eta(2)-C=NCMe=CHS)] 6 whereas with 2 equivalents it gave [Ru-3(mu-H)(2)(CO)(8)(mu-2,3-eta(2)-C=NCMe=CHS)(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 H-1 NMR and infrared spectroscopy and elemental analysis. In addition, the solid-state structures for 1-3 were determined.