Synthesis of new heterometallic complexes by tin–sulfur bond cleavage of pySSnPh3 (pySH = pyridine-2-thiol) at triruthenium and triosmium centres

The ruthenium-tin complex, [Ru(2)(CO)(4)(SnPh(3))(2)(mu-pyS)(2)] (1), the main product of the oxidative-addition of pySSnPh(3) to Ru(3)(CO)(12) in refluxing benzene, is [Ru(CO)(2)(pyS)(SnPh(3))] synthon. It reacts with PPh(3) to give [Ru(CO)(2)(SnPh(3))(PPh(3))(kappa(2)-pyS)] (2) and further with Ru(3)(CO)(12) or [Os(3)(CO)(10)(NCMe)(2)] to afford the butterfly clusters [MRu(3)(CO)(12)(SnPh(3))(mu(3)-pyS)] (3, M=Ru; 4, M=Os). Direct addition of pySSnPh(3) to [Os(3)(CO)(10)(NCMe)(2)] at 70 degrees C gives [Os(3)(CO)(9)(SnPh(3))(mu(3)-pyS)] (5) as the only bimetallic compound, while with unsaturated [Os(3)(CO)(8){mu(3)-PPh(2)CH(2)P(Ph)C(6)H(4)}(mu-H)] the previously reported [Os(3)(CO)(8)(mu-pyS)(mu-H) (mu-dppm)] (6) and the new bimetallic cluster [Os(3)(CO)(7)(SnPh(3)){mu-Ph(2)PCH(2)P(Ph)C(6)H(4)}(mu-pyS)[(mu-H)] (7) are formed at 110 degrees C. Compounds 1, 2, 4, 5 and 7 have been characterized by X-ray diffraction studies. (C) 2010 Elsevier B.V. All rights reserved.