Synthetic Route of Trithiolato-Bridged Dinuclear Arene Ruthenium(II) Complexes [(η6-P-MeC6H4Pri)2Ru2(μ2-SR)3]+

Several dinuclear trithiophenolato-bridged arene ruthenium complexes [(η6-p-MeC6H4Pri)2Ru2(μ2-SC6H4-R)3]+ could so far only be obtained with moderate 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 trithiolato complexes are obtained either only with bad yields or not at all. We employ density functional theory (DFT) calculations to gain a fundamental understanding of the reaction mechanisms leading to the formation of trithiolato complexes starting from the dichloro(p-cymene)ruthenium(II) dimer [(η6-p-MeC6H4Pri)Ru(μ2-Cl)Cl]2. The results of this DFT study enable us to rationalize experimental results and allow us, via a modified synthetic route, to synthesize the previously unreported and hitherto considered as unrealistic trithiolato complex [(η6-p-MeC6H4Pri)2Ru2(μ2-SC6H11)3]+. Our DFT study opens possibilities for the synthesis of so far inaccessible thiolato-bridged dinuclear arene ruthenium(II) complexes but more generally also the synthesis of other thiolato-bridged dinuclear group 8 and 9 metal com-plexes could be reexamined.