Transient resonance Raman and density functional theory investigation of the chlorine atom/carbon disulfide molecular complex involved in selective alkane photochlorination reactions

Abstract

The structure and bonding of the chlorine atom/carbon disulfide (CS2/Cl) complex involved in selective photochlorination reactions with alkanes was directly probed using transient resonance Raman spectroscopy. The experimental Raman vibrational frequencies were compared to those computed from density functional theory calculations for probable structures of the CS2/Cl complex. Our results indicate that the S=C=S···Cl complex species is responsible for the ∼370 nm transient absorption band observed after ultraviolet photolysis of CCl4 in the presence of CS2. We discuss the structure and properties of the S=C=S···Cl complex and compare them with those for the related benzene/Cl and pyridine/Cl complexes.