Reaction of dimeric complex [Rh(CO)(2)Cl](2) with two niolar equivalent of pyridine alcohol ligands (L) like 2-hydroxymethylpyridine (a), 3-hydroxymethylpyridine (b) and 4-hydroxymethylpyridine (c) afford the rhodium(I) dicarbonyl complexes [Rh(CO)(2)CIL](1a-c). The ligands are coordinated to the metal center through N-donor site. The complexes I undergo oxidative addition (OA) reactions with various alkyl halides (RI) like CH3I,C2H5I to produce Rh(III)complexes of the type [Rh(CO)(COR)ICIL], where R= -CH3(2). -C2H5(3). Kinetic data for the reaction of I with CH3I indicate a first order reaction. The catalytic activity of the complexes I in the carbonylation of methanol was higher than that of the well known species [Rh(CO)(2)I-2](-) (C) 2008 Elsevier B.V. All rights reserved.