The invention relates to a catalytic process for the synthesis of an alcohol by reaction of an epoxide with a nucleophilic compound containing a labile hydrogen, such as an alcohol, a phenol, a primary amine or a carboxylic acid.The catalyst is a metal complex of general formula (I)[M[Co(CO).sub.4 ].sub.2 ].sub.x in which x is equal to 1 or 2 and M denotes tin, lead and cadmium.The reaction preferably takes place in the presence of carbon monoxide.This process makes it possible to increase the yield and the selectivity of the reaction and the stereoselectivity for alcohol in the case of which the hydroxyl formed is attached to the least hindered carbon atom of the epoxide.The invention also relates to the new complexes of formula (I) in which x equals 2.It also relates to a process for the electrosynthesis of these new compounds by electroreduction of Co.sub.2 (CO).sub.8 in an organic solvent medium in a cell in which the anode consists of the metal M, followed by isolation of the complex, the temperature of the reaction mixture and that at which the complex is isolated being lower than 25.degree. C.