Matrix isolation study of the thermal and photochemical reaction of OVCl 3 and CrCl 2O 2 with cycloalkylamines

Abstract

The matrix isolation technique has been combined with infrared spectroscopy and theoretical calculations to identify and characterize the initial and secondary products in the thermal and photochemical reactions of OVCl 3 and CrCl 2O 2 with cyclopropyl-, cyclobutyl- and cyclopentylamine. Initial twin jet deposition led to the formation of two new species, the 1:1 molecular complex and the secondary HCl elimination product (e.g. Cl 2V(O)N(H)C 3H 5), as well as free HCl. Overall, the yield decreased with the size of the cycloalkyl ring, to the point with cyclopentylamine, the yield was extremely low and no firm conclusions could be reached. The complexes appear to be moderately strongly bound, leading to shifts to certain vibrational modes of both the acid and base subunits. Bands due to the complexes were destroyed by near-UV irradiation (λ>300 nm), and led an increase in the intensity of the bands due to the HCl elimination product, as well as cage-paired HCl. Theoretical calculations were used to aid in product identification and band assignments.