Interaction of Mo(CO)₆ and its derivative fragments with the Cu(001) surface: Influence on the decomposition process

Abstract

A theoretical study on the adsorption and decomposition of molybdenum carbonyl on the copper (001) surface is reported. The adsorption structures and energies of Mo(CO) n molecules (n 5 1 . . . 6) are computed systematically using density functional theory with Van der Waals corrections. By analyzing the energies of the various conformations, the main factors that determine the stable adsorption geometry are identified. Insight into the thermodynamics of decomposition is gained by calculating the reaction energy for dissociation of Mo(CO) n into Mo(CO) n21 and CO. In the gas phase, this reaction is highly endothermic for all n. On the Cu surface, however, removal of the first CO group (n 5 6) becomes strongly exothermic. The subsequent dissociation steps (n < 6), are endothermic even on the surface, but the reaction energies are much reduced. Dissociation is found energetically more favorable than desorption in all cases. The results clearly show that molybdenum carbonyl decomposition is strongly facilitated by the presence of the Cu surface.

Metal-catalyzed coupling/carbonylative cyclizations for accessing dibenzodiazepinones: an expedient route to clozapine and other drugs

“…Molybdenum hexacarbonyl (Mo(CO) 6 ), was shown to be a powerful CO surrogate in this carbonylative intramolecular cyclization. The efficacy of Mo(CO) 6 is due to the energetically favorable dissociation of Mo(CO) n into Mo(CO) n −1 which was proven to be a highly exothermic reaction in the presence of metal catalysts especially after the dissociation of the first CO group [ 23 ].…”