Argon matrix isolation study of the interaction of VCl 4 with (CH 3) 2CO

Abstract

The matrix isolation technique, combined with infrared spectroscopy and theoretical calculations, has been employed to explore the reaction chemistry of the VCl 4/(CH 3) 2CO system. Initial twin jet deposition led to formation of an isolated 1:1 complex between the subunits. This complex was characterized by strongly shifted C O and V–Cl stretching modes, as well as by lesser perturbations to additional modes of acetone. Theoretical calculations determined a binding energy for the complex of Δ E 0 298=−4.3 kcal/mol at the UB3LYP/6-31++G(d,2p) level of theory. Calculated infrared spectra, including deuterium shifts, were overall in good agreement with the experimental spectra. Bands due to the complex grew upon annealing, as well as upon irradiation prior to annealing. Matrices irradiated after annealing showed no change. This result differs markedly from the chemistry of the OVCl 3/(CH 3) 2CO system, and demonstrates the role of the oxo group in the reaction chemistry.