The reactions of [Rh-2(DTolF)(2)(CH3CN)(6)][BF4](2) (1) (DTolF = N,N-di-p-tolylformamidinate) with 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen) proceed with substitution of CH3CN molecules to give products with the N-N ligands chelating in an equatorial-equatorial (eq-eq) fashion. Compound 1 reacts with 1 equiv of bpy to yield a mixture of [Rh-2(DTolF)(2)(bpy)(CH3CN)(3)][BF4](2).(CH3)(2)CO (2a) and [Rh-2(DTolF)(2)(bpy)(CH3CN)(4)][BF4](2) (2b). Compound 2a crystallizes in the monoclinic space group P2(1)/n with a = 13.5856(2) Angstrom, b = 18.0402(2) Angstrom, c = 21.4791(3) Angstrom; alpha = 90degrees, beta = 101.044(1)degrees, gamma = 90degrees; V = 5167.27(12) Angstrom(3), Z = 4, R = 0.0531, and R-w = 0.0948. Compound 2b crystallizes in the monoclinic space group P2(1)/n with a = 10.9339(2) Angstrom, b = 24.4858(l) Angstrom, c = 19.4874(3) Angstrom; alpha = 90degrees, beta = 94.329(l)degrees, gamma = 90degrees; V = 5202.38(13) Angstrom(3), Z = 4, R = 0.0459, and R-w = 0.1140. The reaction of compound 1 with 2 equiv of bpy affords [Rh-2(DTolF)(2)(bpy)(2)(CH3CN)][BF4](2) (3) which crystallizes in the monoclinic space group P2(1)/a with a = 19.4534(4) Angstrom, b = 13.8298(3) Angstrom, c = 19.8218(5) Angstrom; alpha = 90degrees, beta = 109.189(l)degrees, gamma = 90degrees; V = 5036.5(2) Angstrom(3), Z = 4, R = 0.0589, and R-w = 0.0860. Compound 1 reacts with 1 equiv of phen to form [Rh-2(DTolF)(2)(phen)(CH3CN)(3)][BF4](2).2C(2)H(5)OC(2)H(5) (4) which crystallizes in the triclinic space group P (1) over bar with a = 12.6346(2) Angstrom, b = 13.5872(2) Angstrom, c = 19.0597(3) Angstrom; alpha = 71.948(l)degrees, beta = 73-631 (1)degrees, gamma = 71.380(l)degrees; V = 2886.70(8) Angstrom(3), Z = 2, R = 0.0445, and R-w = 0.1207. A notable feature of the cations in 2a, 3, and 4 is the presence of only one axial (ax) CH3CN ligand, a fact that can be attributed to the steric effect of the formamidinate bridging ligands. Compounds 2a, 2b, 3, and 4 were fully characterized by X-ray crystallography and H-1 NMR spectroscopy, whereas [Rh-2(DTolF)(2)(phen)(2)(CH3CN)(2)][BF4](2) (5) was characterized by H-1 NMR spectroscopy.