The reactions of chloro-bridged dimeric complexes [{(η 3 ;η 3 -C 10 H 16 )Ru(μ-Cl)Cl} 2 ] and [{(η 4 -C 8 H 12 )RhCl} 2 ] with 1-(4-cyanophenyl)imidazole (CPI), 1-(4-nitrophenyl)imidazole (NOPI), 1-(4-formylphenyl)imidazole (FPI) and 1-(4-hydroxy-phenyl)imidazole (HPI) have been investigated. These reactions afforded complexes with the general formulations [(η 3 ;η 3 -C 10 H 16 )RuCl 2 (L)] (L=CPI, 1; NOPI, 2; FPI, 3; HPI, 4) and [(η 4 -C 8 H 12 )RhCl(L)] (L=CPI, 5; NOPI, 6; FPI, 7; HPI, 8). Resulting complexes have been characterized by analytical and spectral (IR, 1 H and 13 C NMR, UV–Vis) studies. Crystal structures of 2, 5 and 6 have been determined by single crystal X-ray diffraction analyses. Structural studies on the complexes 2, 5 and 6 revealed the presence of extensive inter- and intra-molecular C–H⋯X (X=O and Cl) and C–H⋯π interactions. Theoretical studies have been performed to authenticate the structures and NBO calculations to determine electronic properties of the complexes.