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

Abstract

Several dinuclear thiophenolato-bridged arene ruthenium complexes [(η6-p-MeC6H4Pri)2Ru2(μ2-SC6H4-R)3]+ could so far only<br>be obtained with moderate yields using the synthetic route established in the early 2000s. With much less reactive aliphatic<br>thiols or with bulky thiols, the reactions become even less efficient and the desired complexes are obtained with low yields<br>or not at all. We employed density functional theory (DFT) calculations to gain a fundamental understanding of the reaction<br>mechanisms leading to the formation of dithiolato and trithiolato complexes starting from the dichloro(pcymene)<br>ruthenium(II) dimer [(η6-p-MeC6H4Pri)Ru(μ2-Cl)Cl]2. The results of the DFT study enabled us to rationalise<br>experimental results and allowed us, via a modified synthetic route, to synthesise previously unreported and hitherto<br>considered as unrealistic complexes. Our study opens possibilities for the synthesis of so far inaccessible thiolato-bridged<br>dinuclear arene ruthenium(II) complexes but more generally also the synthesis of other thiolato-bridged dinuclear group 8<br>and 9 metal complexes could be reexamined.