Synthesis and reactivity of mono-, tri-, and poly-nuclear ruthenium carbonyl complexes containing the pyridine-2-thiolate ligand (pyS). Stepwise preparation of [Ru(pyS) 2 (CO) 2 ] by reaction of [Ru 3 (CO) 12 ] with pyridine-2-thiol

The thermal reaction of [Ru3(CO)12] with pyridine-2-thiol (pySH) gives the trinuclear complex [Ru3(µ-H)(µ3-pyS)(CO)9](1), which is subsequently converted into the polymer [{Ru(µ3-pyS)(CO)2}n](2). Further reaction of polymer (2) with pyridine-2-thiol gives the monomeric compound [Ru(pyS)2(CO)2](3). Complexes (1) and (2) contain triply bridging pyS ligands while in complex (3) both pyS ligands are chelating. These results indicate that the reactivity of [Ru3(CO)12] with pyridine-2-thiol is different to that found for [Os3(CO)12] and for [Ru3(CO)12] with 2-aminopyridine and 2-hydroxypyridine. The reactions of complexes (1)–(3) with several P-donor ligands are also described. Infrared and 1H and 31P-{1H} n.m.r. spectral data for all the compounds are presented and discussed in relation to their structures.