Experimental Identification of the Active Site in the Heteronuclear Redox Couples [AlVOx](+.)/CO/N2O (x=3,4) by Gas-Phase IR Spectroscopy

摘要

Cryogenic ion vibrational spectroscopy was used in combination with electronic structure calculations to identify the active site in the oxygen atom transfer reaction [AlVO4](+.)+CO[AlVO3](+.)+CO2. Infrared photodissociation spectra of messenger-tagged heteronuclear clusters demonstrate that in contrast to [AlVO4](+.), [AlVO3](+.) is devoid of a terminal Al-O-t unit while the terminal V=O-t group remains intact. Thus it is the Al-O-t moiety that forms the active site in the [AlVOx](+.)/CO/N2O (x=3, 4) redox couples, which is in line with theoretical predictions.