Transition metal complexes with sulfur ligands, 142 - Inert and labile [Ru(L)('pyS(4)')] complexes with rigid [RuNS4] cores and trans-thiolate donors[L = PPh3, PEt3 DMSO, CO, NO+, N2H4; 'pyS(4)'(2-)=2,6-bis(2-mercaptophenylthio)dimethylpyridine(2-)]

In a quest for ruthenium complexes having [RuNS4] cores, a non-fluxional co nfiguration, trans-thiolate donors, and exchangeable coligands L, [Ru(L)('p yS(4)')] complexes have been synthesized ['pyS(4)'(2-) = 2,6-bis(2-mercapto phenylthio)dimethylpyridine(2-)]. Treatment of [RuCl2(PPh3)(3)] with 'pyS(4 )'(2-) gave [Ru(PPh3)('pyS(4)')] (1). Alkylation of 1 with excess MeI yield ed [Ru(PPh3)('pyS(4)'-Me-2)]I-2 (2). [Ru(DMSO)('pyS(4)')] (3) was obtained from [RuCl2(DMSO)(4)] and 'pyS(4)'(2-). The PPh3 or DMSO coligands in 1, 2, and 3 proved to be very inert to substitution. Only the DMSO could be disp laced by CO under drastic conditions yielding [Ru(CO)('pyS(4)')] (4). Treat ment of [RuCl2(CH3CN)(4)] with 'pyS(4)'(2-) yielded [Ru('pyS(4)')](2) (5); in the presence of PEt3 or N2H4 mononuclear [Ru(PEt3)('pyS(4)')] (6) and [R u(N2H4)('pyS(4)')] (7) were formed. Template alkylation of NBu4[Ru(NO)(S2C6 H4)(2)] with 2,6-bis(tosyloxy methyl)pyridine gave [Ru(NO)('pyS(4)')]Tos (8 ). Complex 8 proved to be the best suited precursor for L exchange reaction s. Under reducing conditions, 8 releases its NO ligand and the resulting [R u('pyS(4)')] fragments can combine either with each other to give 5, or wit h PEt3 and N2H4 to yield 6 and 7, respectively. All complexes have been cha racterized by spectroscopic methods and elemental analysis; 1, 2, 3, and 4 have also been submitted to X-ray structure analysis.