A novel homologous series of Rh{sub 2}(0,0), Rh{sub 2}(0,II), and Rh{sub 2}(II,II) bis(difluorophosphino)methylamine complexes have been synthesized and structurally and electronically characterized. These binuclear rhodium compounds are all prepared from the reaction of (RhCl(PF{sub 3}){sub f2}){sub 2} with CH{sub 3}N(PF{sub 2}){sub 2}. Under reducing conditions, Rh{sub 2}(CH{sub 3}N(PF{sub 2}){sub 2}){sub 3}(PF{sub 3}){sub 2} (1) is isolated in moderate yields. Orange crystals of 1, prepared by layering hexane over a dichloromethane solution of 1, are triclinic with a space group P{anti 1}, a = 10.021 (4) {angstrom}, b = 10.139 (4) {angstrom}, c = 14.299 (7) {angstrom}, {alpha} = 74.95 (3){degree}, {beta} = 76.79 (3){degree}, {gamma} = 62.17 (3){degree}, V = 1,230.9 (9) {angstrom}{sup 3}, and Z = 2. In the absence of oxidants and reductants, the unsymmetrical mixed-valence Rh{sub 2}(CH{sub 3}N(PF{sub 2}){sub 2}){sub 3}Cl{sub 2}(PF{sub 3}) (2) complex is obtained. The molecular structure of 2 is a composite of 1 and 3 in that the trigonal-bipyramidal coordination geometry about Rh(0) centers in 1 and the octahedral coordination at the Rh(II) centers in 3 are retained about the mixed-valence Rh{sub 2}(0,II) core.