Compounds [Re(bipy)(CO)(3)(HIm)]OTf (1) and [Mo(η(3)-C(3)H(4)-R-2)(CO)(2)(HIm)(phen)]BAr'(4) [R = Me (2a), H (2b); Ar' = 3,5-bis(trifluoromethyl)phenyl; HIm = 1H-imidazole] were prepared from 1H-imidazole and either [Re(OTf)(bipy)(CO)(3)] or [MoCl(η(3)-C(3)H(4)-R-2)(CO)(2)(phen)]. Compounds 1, 2a, and 2b were deprotonated to afford the terminal κ-N-imidazolate complexes [Re(bipy)(CO)(3)(Im)] (3) and [Mo(η(3)-C(3)H(4)-R-2)(CO)(2)(Im)(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)(μ-Im)]OTf (5), [{Mo(η(3)-C(4)H(7))(CO)(2)(phen)}(2)(μ-Im)]OTf (6), and [{Mo(η(3)-C(3)H(5))(CO)(2)(phen)}(μ-Im){Re(phen)(CO)(3)}]OTf (7). The reaction of [Mo(η(3)-C(4)H(7))(CO)(2)(Im)(phen)] (4a) with SnClPh(3) led to the formation of the trinuclear complex [{Mo(η(3)-C(4)H(7))(CO)(2)(phen)(μ-Im)}(2){SnPh(3)}]BAr'(4) (8).
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