Density functional theory investigations of the reaction of the chlorine atom-carbon disulfide molecular complex with dimethylbutane: Implications for tertiary selectivity in alkane photochlorination reactions

A density functional theory investigation of the chemical reactivity of the S=C=S...C1 complex toward 2,3-dimethylbutane (DMB) has been reported and compared to the related reaction of a C1 atom with DMB. The DFT calculations indicate that the reaction of C1 atom with DMB would have little tertiary selectivity toward chlorination consistent with experimental results for photochlorination of alkanes in invert solvents.