Transition Metal Complexes with Sulfur Ligands, 142 Inert and Labile [Ru(L)('pyS_4')] Complexes with Rigid [RuNS_4] Cores and trans-Thiolate Donors [L = PPh_3, PEt_3, DMSO, CO, NO~+, N_2H_4; 'py S_4'~(2-) = 2, 6-Bis(2-mercaptophenylthio)dimethylpyrid

摘要

In a quest for ruthenium complexes having [RuNS_4] cores, a non-fluxional configuration, trans-thiolate donors, and exchangeable coligands L, (Ru(L)('pyS_4')] complexes have been synthesized ['pyS_4'~(2-) = 2, 6-bis(2-mercaptophenylthio)dimethylpyridine(2-)]. Treatment of [RuCl_2(PPh_3)_3] with 'pyS_4'~(2-) gave [Ru(PPh_3)('pyS_4')] (1). Alkylation of 1 with excess MeI yielded [Ru(PPh_3)('pyS_4'-Me_2)]I_2 (2). [Ru(DMSO)('pyS_4')] (3) was obtained from [RuCl_2(DMSO)_4] and 'pyS_4'~(2-). The PPh_3 or DMSO coligands in 1,2, and 3 proved to be very inert to substitution. Only the DMSO could be displaced by CO under drastic conditions yielding [Ru(CO)('pyS_4')] (4). Treatment of [RuCl_2(CH_3CN)_4] with 'pyS_4'~(2-) yielded [Ru('pyS_4')]_2 (5); in the presence of PEt_3 or N_2H_4 mononuclear [Ru(PEt_3)('pyS_4')] (6) and [Ru(N_2H_4)('pyS_4')] (7) were formed. Template alkylation of NBu_4[Ru(NO)(S_2C_6H_4)_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 reactions. Under reducing conditions, 8 releases its NO ligand and the resulting [Ru('pyS_4')] fragments can combine either with each other to give 5, or with PEt_3 and N_2H_4 to yield 6 and 7, respectively. All complexes have been characterized by spectroscopic methods and elemental analysis; 1, 2, 3, and 4 have also been submitted to X-ray structure analysis.