The synthesis and characterization of products from reactions of Rh-2(form)(2)(O2CCF3)(2)(CH3CN)(2) (form = N,N'-p-ditolylformamidinate, N,N'-diphenylformamidinate) and the partially solvated [Rh-2(DTolF)(2)(CN3CN)(6)] [BF4](2) (DtolF = N,N'-p-ditolylformamidinate) with the DNA purine analogues, 9-ethylguanine, and 9-ethyladenine are described. X-ray crystallography was used to characterize Rh-2(DTolF)(2)(O2CCF3)(2)(CH3CN)(2) (1) which crystallizes in the space group P2(1)/n with a 10.849 (3) Angstrom, b = 21.435 (6) Angstrom, c = 18.677 (3) Angstrom, V = 4340 Angstrom(3), Z = 4, R = 0.0451, and R-w = 0.0904. The two rhodium centers are bridged by four O2CCF3- ligands with a Rh-Rh distance of 2.24743(5) Angstrom. Compound 1 reacts with 9-ethylguanine to form Rh-2(DTolF)(2)(9-EtGH)(2)(O2CCF3)(2) (3) which exists as two isomers, namely head-to-head and head-to-tail as confirmed by H-1 NMR spectroscopy. [Rh-2(DTolF)(2)(CH3CN)(6)] [BF4](2) (5) crystallizes in the Pbca space group with a = 21.646 (3) Angstrom, b = 31.272 (3) Angstrom, 14.561(4) Angstrom, V = 9857 Angstrom(3), Z = 8, R = 0.036, and R-w = 0.063. The Ph-Ph bond distance is 2.5594 (8) Angstrom. The partially solvated compound 5 reacts with 9-ethyladenine and 9-ethylguanine to form [Rh-2(DTolF)(2)(9-EtAH)(2)(CH3CN)] [BF4](2) (6) and [Rh-2(DTolF)(2)(9-EtGH)(2)(CH3CN)][BF4](2) (7), respectively. Compound 6 was characterized by X-ray crystallography as well as by variable temperature H-1 NMR spectroscopy. [Rh-2(DTolF)(2)-(9-EtAH)(2)(CH3CN)] [BF4](2) crystallizes in the P2(1)/c space group with a 15.648(8) Angstrom, b = 16.575(5) Angstrom, c 20.026(8) Angstrom, beta = 105.17(4)degrees, V = 4994 Angstrom(3), Z = 4, R = 0.063, and R-w = 0.073. This compound contains two bridging DTolF(-) ligands as well as two 9-ethyladenine ligands bridging through the N7 and exocyclic N6 positions in a head-to-tail fashion. H-1 NMR studies performed on 6 revealed that the N6 position is in the imino (NH-) form.