Direct observation of an isopolyhalomethane O-H insertion reaction with water:Picosecond time-resolved resonance Raman (ps-TR~3) study of the isobromoform reaction with water to produce a CHBr_2 OH product

摘要

Picosecond time-resolved resonance Raman (ps-TR~3) spectroscopy was used to obtain the first definitive spectroscopic observation ofa n isopolyhalomethane O-H insertion reaction with water.The ps-TR~3 spectra show that isobromoform is produced within several picoseconds after photolysis of CHBr_3 and then reacts on the hundreds of picosecond time scale with water to produce a CHBr_2OH reaction product.Photolysis of low concentrations of bromoform in aqueous solution resulted in noticeable formation of HBr strong acid.Ab initio calculations show that isobromoform can react with water to produce a CHBr_2(OH)-H insertion reaction product and a HBr leaving group.This is consistent with both the ps-TR~3 experiments that observe the reaction of isobromoform with water to form a CHBr_2 (OH) product and photolysis experiments that show HBr acid formation.We briefly discuss the implications of these results for the phase dependent behavior of polyhalomethane photochemistry in the gas phase versus water solvated environments.