The acetonitrile ligands in [(PhB(CH2PPh2)(3)-kappa P-3)-Ru(NCMe)(3)]PF6 (1) (which contains a facially coordinated anionic tripodal phosphine ligand) are labile and are rapidly replaced by other ligands, although the steric profile of the phosphine ligand limits the size and the number of the incoming ligands. Complex 1 and some of its derivatives proved to be very efficient and rapid transfer hydrogenation precatalysts and yielded turnover frequencies (TOFs) greater than those typically observed for most other ruthenium-based catalysts.