Reactions of dimeric complex [Rh(CO) 2 Cl] 2 (1) with pyridine ester ligands methyl picolinate (a), methyl nicotinate (b), methyl isonicotinate (c), ethyl picolinate (d), ethyl nicotinate (e) and ethyl isonicotinate (f) in the 1:2 molar ratio afford the complexes of the type [Rh(CO) 2 ClL] (1a-f). The complexes 1a-f exhibit two equally intense ฮฝ(CO) bands in the range 1990-2091 cm -1 indicating cis-disposition of the two terminal carbonyl groups. The complexes 1a and 1d undergo partial decarbonylation reaction in solution to give the corresponding chelated monocarbonyl complexes [Rh(CO)Cl(methyl picolinate)] (1a ) and [Rh(CO)Cl(ethyl picolinate)] (1d ), respectively. The complexes 1a-f undergo oxidative addition reaction with different types of electrophiles like CH 3 I, C 2 H 5 I, C 6 H 5 CH 2 Cl and I 2 to yield [Rh(CO
) and [Rh(CO)ClI 2 L] (5a-f) complexes, respectively. The complexes have been characterized by elemental analysis, IR and 1 H NMR spectroscopy. The time taken by the different complexes 1a-f for the completion of oxidative addition reactions of CH 3 I are different and the complex 1f took the shortest time while the complex 1b required the longest time. The catalytic activity of the complexes [Rh(CO) 2 ClL] (1) in carbonylation of methanol is higher (TON = 844-1251) than the well known [Rh(CO) 2 I 2 ] -species (TON = 653).