The complexes [RuCl(PPh3)(2)(P, N, N'-PPh3-x(py)(x))]PF6 (x = 2, 1b; 3, 1c; py = 2-pyridyl) were isolated from the reaction of RuCl2(PPh3)(3) with 1 equiv of PPh3-x(py)(x) and NH4PF6 in acetone. Crystals of 1b (C52H43ClF6N2P4Ru) are monoclinic, a = 17.795(2), b = 11.375(4), and c = 23.343(2) Angstrom, beta = 97.012(8)degrees, Z = 4, space group P2(1)/c; those for 1c (C51H42ClF6N3P4Ru) are monoclinic, a = 17.812(1), b = 11.353(2), and c = 23.391(1) Angstrom, beta = 97.738(5)degrees, Z = 4, space group P2(1)/c. The isomorphous structures were solved by the Patterson method and were refined by full-matrix least-squares procedures to R = 0.036 and 0.033 (R-W = 0.035 and 0.031) for 7690 and 8121 reflections with I greater than or equal to 3 sigma(I), respectively. The P, N, N'-coordination mode for 2-pyridylphosphines is previously unreported. The P, N-coordinated complexes cis-RuCl2(dppb)(PPh3-x(py)(x)) (x = 1-3; dppb = Ph2P(CH2)(4)PPh2) were made by isomerization of the corresponding trans-dichloro isomers, which are themselves synthesized from RuCl2(dppb)(PPh3). The cis complexes in CHCl3 or CH2Cl2 dissociate chloride reversibly with formation of P, N, N'-coordinated PPh3-x(py)(x) species, which were isolated as [RuCl(dppb)(PPh3-x(py)(x))]PF6 (x = 2, 3). Reactions of CO with the species containing the strained P, N, N'-coordination mode lead to displacement of a coordinated pyridyl and formation of the P, N-coordinated complexes [RuCl(CO)(PP)(PPh3-x(py)(x))]PF6 (PP (PPh3)(2), x = 2, 3; and PP = dppb, x = 2, 3). The CO reactions are partially reversible. Solution structures of the complexes were determined by NMR, LR, and UV-visible spectroscopies and conductivity.