Compounds [Re(bipy)(CO)(3)(Hlm)]OTf (1) and [Mo(eta(3)-C3H4-R-2)(CO)(2)(Hlm)(Phen)]BAr'(4) [R = Me (2a), H (2b); Ar' = 3,5-bis(trifluoromethyl)phenyl; Hlm = 1H-imidazole] were prepared from 1H-imidazole and either [Re(OTf(bipy)-(CO)(3)] or [MoCl(eta(3)-C3H4-R-2)(CO)(2)(Phen)]. Compounds 1, 2a, and 2b were deprotonated to afford the terminal kappa-N-imidazolate complexes [Re(bipy)(CO)(3)(lm)] (3) and [Mo(eta(3)-C3H4-R-2)(CO)(2)(lm)(phen)] [R = Me (4a), H (4b)], which were fully characterized, including an X-ray structural determination of 3. The topological analysis of the electron density (obtained from the X-ray diffraction study) and its Laplacian were used to characterize the differences in the electron density at the five-membered ring ligand between the imidazole and imidazolate complexes 1 and 3. The reaction of complexes 3, 4a, and 4b with the appropriate organometallic complexes afforded the bimetallic imidazolate-bridged compounds [{Re(bipy)(CO)(3)}(2)(mu-lm)]OTf (5), [{Mo(eta(3)-C4H7)(CO)(2)(Phen)}(2)(mu-lm)]OTf (6), and [{Mo(eta(3)-C3H5)(CO)(2)(phen)}(mu-lm){Re(Phen)(CO)(3)}]OTf (7). The reaction of [Mo(eta(3)-C4H7)(CO)(2)(lm)(Phen)] (4a) with SnClPh3 led to the formation of the trinuclear complex [{Mo(eta(3)-C4H7)(CO)(2)(Phen)(mu-lm)}(2){SnPh3}]BAr'(4) (8).