Matrix isolation and theoretical study of the photochemical reaction of CH3CN with CrO2Cl2 and OVCl3

The matrix isolation technique has been combined with theoretical calculations to identify and characterize the photoproducts in the reactions of CH3CN with CrCl2O2 and OVCl3. Twin jet co-deposition of these reagents led to the formation of a 1:1 molecular complex which was observed using UV/visible spectroscopy. Irradiation of these matrices with light of lambda > 300 nm led to the observation of new bands in the infrared spectra, the most intense of which was seen at 1942 cm(-1) for the CrCl2O2/CH3CN system. The product bands are assigned to the (2)eta complexes of acetonitrile n-oxide with CrCl2O and VCl3, respectively. Identification of these species was supported by extensive isotopic labeling (H-2 and N-15), as well as by B3LYP/6-311 + + G(d,2p) density functional calculations. (c) 2005 Elsevier B.V. All rights reserved.