NO Formation via Reductive Disproportionation of NO by Mononuclear Copper Complexes: A Mechanistic DFT Study.

The mechanism of the copper(I)-mediated reductive disproportionation reaction of NO to form NO was investigated for five different 3,5-substituted tris(pyrazolyl)borate copper complexes (CuTp) by means of DFT calculations. A thorough search of the potential surface was performed, using the B3LYP functional with the def2-SVP basis set for optimization purposes and def2-TZVP single-point calculations for constructing the potential energy surface for two of these complexes. The results can be condensed into six competing reaction mechanisms, two of which were more closely investigated using full def2-TZVP optimized potential and free energies. The results consistently predict the same mechanism to have the lowest overall barrier. For all five different complexes, this is found to be in good agreement with the experimental reaction barriers. The key intermediate for the transition from the N-bound reactant to the O-bound product contains a stable (NO) unit with one N-Cu and one O-Cu bond, which was not included in the mechanistic considerations reported in the literature. Further analysis of the charge distribution and the spin density demonstrates the formation of a Cu(II)-(NO) intermediate and the electronic influence of the different ligands.