Synthesis and Resolution of Chiral Ruthenium Complexes Containing the 1‑Me-3-PhCp Ligand

A new ruthenium chloride complex featuring chirality derived from the face-specific coordination of the 1-Me-3-PhCp ligand has been successfully synthesized and resolved. The resolution has been achieved via the diastereomers of the (S)-α-methyl-benzenemethanethiolate complex (1-Me-3-PhCp)­Ru­(dppm)­{(S)-C­(S)­(H)­(Ph)­(Me)}. The X-ray structures of (SCp,S)-(1-Me-3-PhCp)­Ru­(dppm)­{C­(S)­(H)­(Ph)­(Me)} and (RCp,S)-(1-Me-3-PhCp)­Ru­(dppm)­{C­(S)­(H)­(Ph)­(Me)} have been determined. Racemization has been observed at elevated temperatures, but a room-temperature conversion pathway provides access to the corresponding enantiopure acetonitrile, chloride, and hydride complexes.