P-31 CP/MAS NMR spectroscopy is examined as a method of characterization for ruthenium(II) phosphine complexes in the solid state, and the results are compared with X-ray crystallographic data determined for RuCl2(dppb)(PPh(3)) (dppb = Ph(2)P(CH2)(4)PPh(2)), RuBr2(PPh(3))(3), and the previously determined RuCl2(PPh(3))(3). Crystals of RuBr2(PPh(3))(3) (C54H45Br2P3Ru) are monoclinic, space group P2(1)/a, with a = 12.482(4) Angstrom, b = 20.206(6) Angstrom, c = 17.956(3) Angstrom, beta = 90.40(2)degrees, and Z = 4, and those of RuCl2(dppb)(PPh(3)) (C46H43Cl2P3Ru) are also monoclinic, space group P2(1)/n, with a = 10.885(2) Angstrom, b = 20.477(1) Angstrom, c = 18.292(2) Angstrom, beta = 99.979(9)degrees, and Z = 4. The structure of RuBr2(PPh(3))(3) was solved by direct methods, and that of RuCl2(dppb)(PPh(3)) was solved by the Patterson method. The structures were refined by full-matrix least-squares procedures to R = 0.048 and 0.031 (R(w) = 0.046 and 0.032) for 5069 and 5925 reflections with I greater than or equal to 3 sigma(I), respectively. Synthetic routes to RuBr2(dppb)(PPh(3)) and [RuBr(dppb)](2)(mu(2)-dppb) are reported. The reactivity of RuCl2(dppb)(PPh(3)) with the neutral two-electron donor ligands (L) dimethyl sulfoxide, tetramethylene sulfoxide, tetrahydrothiophene, and dimethyl sulfide to give [(L)(dppb)Ru(mu-Cl)(3)RuCl(dppb)] is discussed.