Matrix isolation and density functional studies of novel transition metal complexes. NO + Fe, Co, Ni, Cu, and Zn in argon matrices

Abstract

We have undertaken a study of the interaction and reaction of nitric oxide with the first row transition metal atoms. Such studies are applicable to catalytic processes (i.e. NO x reduction) as well as direct corrosion of metals. NO and transition metal vapors were trapped in cryogenic argon matrices and their interactions were probed using FTIR spectroscopy. A number of complexes of varying stoichiometry were detected; however, there was no detectable interaction between NO and Zn. Density functional studies using several functional combinations were performed to determine structures, vibrational frequencies, and binding energies of the MNO complexes. There is no obvious discernible trend in the binding properties across the row. DFT calculations do support the Zn NO results by predicting a negative binding energy for the ZnNO complex. A comparison with MCO complexes is offered.