Dinuclear thiolato-bridged arene ruthenium complexes: from reaction conditions and mechanism to synthesis of new complexes.

Several dinuclear thiophenolato-bridged arene ruthenium complexes [(η--MeCHPr)Ru(μ-SCH-R)] (R = H, NO, F) could so far only be obtained in fair yields using the synthetic route established in the early 2000s. With much less reactive aliphatic thiols or with bulky thiols, the reactions become even less efficient and the desired complexes are obtained with low yields or not at all. We employed density functional theory (DFT) calculations to gain a fundamental understanding of the reaction mechanisms leading to the formation of dithiolato and trithiolato complexes starting from the dichloro(-cymene)ruthenium(ii) dimer [(η--MeCHPr)Ru(μ-Cl)Cl].