A novel mechanism for the gas-phase Fe(CO)(5) and base catalyzed water gas shift reaction has been examined. The reaction pathway described here is predicted at the B3LYP/6-31++G(d,p) level to be energetically competitive with the classic mechanism. The reaction path explored here involves the energetically barrierless formation of (CO)(4)FeCOOH- (the catalyst of the system) decarboxylation induced by the addition of CO to give (CO)(4)FeCHO, and evolution of H-2 upon addition of H2O to the (CO)(4)FeCHO intermediate. The energetic barriers predicted for the last two steps are 21.2 and 42.0 kcal/mol, respectively, using the B3LYP method.