Infrared matrix isolation study of the reaction of CrCl2O2 with (CH3)2O and (CH3)2CO

Abstract

Matrix isolation has been combined with infrared spectroscopy to study the reaction chemistry of CrCl2O2 with (CH3)2O and (CH3)2CO. Very similar results were obtained with twin jet and room temperature merged jet deposition, indicating that the initial product forms on the surface of the matrix during deposition, not in the deposition lines prior to matrix condensation. The initial product in both systems was identified as the 1:1 complex between the two reagents, with a structure in which the oxygen atom of the base donates electron density to the Cr center. A number of perturbed vibrational modes of both subunits were observed; for the bases, these modes were vibrations involving the oxygen atom. Hg arc irradiation of the CrCl2O2·O(CH3)2 complex led to growth of a secondary product that is tentatively identified as Cl2CrO(OCH3)2. The CrCl2O2·OC(CH3)2 complex was not photosensitive, and no rearrangements were observed.