TRIOSMIUM AND TRIRUTHENIUM CLUSTERS CONTAINING THE 4-METHYLTHIAZOLIDELIGAND - CRYSTAL-STRUCTURES OF [OS-3(MU-H)(CO)(10)(MU-2,3-ETA(2)-C=NCME-CHS)], -3(MU-H)(CO)(9)(MU-2,3-ETA(2)-C=NCME=CHS)(PPH(3))] AND 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 th e nitrogen and carbon atoms of the C=N bond, in high yield. Compound 1 reacted with PPh(3) at 110 degrees C to give -3(mu-H)(CO)(9)(mu-2,3-e ta(2)-C=NCMe=CHS)(PPh(3))] 2 and 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 yield ed 3 in good yield. Compound 1 reacted with 4-methylthiazole at 110 de grees C to give -2,3-eta(2)-C=NCMe=CHS)(mu-1,5-eta(2)-CH=NCMe=CS)] 4 a nd Os-3(mu-H)(2)(CO)(8)(mu-2,3-eta(2)-C=NCMe=CHS)(2)] 5. In 4 the seco nd thiazolide ligand is co-ordinated through the sulfur and C(5) carbo n atoms whereas in 5 both ligands are co-ordinated through the nitroge n and C(2) carbon atoms. The reaction of [Ru-3(CO)(12)] with 1 equival ent of 4-methylthiazole in the presence of sodium-benzophenone at 67 d egrees 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 analy sis. In addition, the solid-state structures for 1-3 were determined.