Spectroscopy and computations of supported metal adducts. 1. DFT Study of CO and NO adsorption and coadsorption on Cu/SiO2

Interactions of the CO and NO molecules with the Cu(II) and Cu(I) isolated sites on the amorphous silica surface are investigated by means of density functional theory (DFT) methods within the finite cluster model approach. The clusters of silica of increasing nT size (T = Si) are used, with n from 2 to 6. The Cu(II) sites are characterized by calculated g-tensors and hyperfine coupling constants (HFCCs) and compared with experiment. On this basis, the three-coordinated complexes are the most plausible. Due to the charge transfer from the silica "ligand", the metal charge shrinks and the spin density is distributed over silanol and siloxy groups up to 50%. The reduced sites are exclusively two-coordinated. Strong interaction of CO with Cu(I)-nT sites (31-39 kcal/mol) gives rise to the formation of carbonyl adducts with planar coordination around copper. The population of the ligand pi system shifts downward the stretching frequency in agreement with experiment. Reaction with a second CO molecule gives a geminal dicarbonyl of very uniform structure independent of the site. Carbonyl complexes with Cu(II) are less stable and of tetrahedral coordination of the metal. Accumulation of the positive charge on the complex along with sigma overlap with d orbitals locates the calculated CO stretching frequency above free molecule value. NO molecule is preferably bound to the Cu(II)-nT sites, forming a tetrahedral complex with tilted adsorbate and NO stretching frequency blue-shifted with respect to the free molecule value. The full set of electron paramagnetic resonance (EPR) parameters and vibrational frequencies for the copper(I) mononitrosyl, {CuNO}(11), though not observed experimentally, are predicted and compared to the same magnetophore inside the ZSM-5 zeolite. The interaction energies show that in the CO/NO reaction mixture adsorption is selective and allows discrimination between Cu(I) and Cu(II) sites. However, for the Cu(I) complex, formation of mixed-ligand structures of the {Cu(CO)(NO)}(11) type is possible.