Secondary phosphine complexes of the formula [(eta(5)-C5H5)Ru(L)(2)(PHR2)](+) BArF- are prepared from cationic ruthenium N-2 complexes and PHR2 (R = Ph (a), t-Bu (b), Cy (c)). Additions of t-BuOK or NaN(SiMe3)(2) give the phosphido complexes (eta(5)-C5H5)Ru(L)(2)(PR2) ((L)(2) = (PEt3)(2) (5a-c), depe (6a,b)) in high NMR yields. These rapidly oxidize in air to give isolable RuP(=O)R-2 species, Complex 5a is more basic than the rhenium analogue (eta(5)-C5H5)Re(NO)(PPh3)(PPh2), and 6b is more basic than P-t-Bu-3 Complexes 5a-c and 6b are effective ligands for palladium-catalyzed Suzuki reactions. The catalyst from 6b is nearly as reactive as that from the benchmark ligand P-t-Bu-3.