Matrix Isolation Investigation of the Vibrational and Electronic Spectroscopy and Photochemistry of Complexes of ClF and Cl2 with Sulfide Bases

Article abstract of DOI:10.1021/j100292a013

Matrix isolation has been coupled with twin jet deposition for the formation of 1:1 molecular complexes of ClF and Cl2 with dimethyl sulfide and related bases.The infrared spectra of the complexes were dominated by an intense absorption which has been assigned to the perturbed halogen streching mode.This mode was greatly intensified and red-shifted upon complexes formation; the observed shifts of up to 300 cm^-1 were much greater than shifts for the complexes of ClF with oxigen bases.The spectral differences have been rationalized in terms of hard/soft acid/base theory.Visible-ultraviolet spectra were also recorded for these complexes at high dilutions; for several an intense charge-transfer band was observed in the UV.Mercury arc irradiation into this charge-transfer absorption led to photochemically induced rearrangement reactions for several of complexes studied.