Density Functional Theory Investigation on the Reaction Mechanisms of Ti (3F) with CH2Cl2 and CHCl3 to CH2=TiCl2 and HC÷TiCl3

摘要

The reaction mechanisms of Ti（3F） + CH2C12→CH2=TiCl2 and Ti（3F） + CHC13→HC÷TiCl3 were investigated with Gaussian 03 program package at the B3PW91/6-311++G（d,p）level.The computational results revealed that:1) Both reaction systems are initiated by Ti（3F） atom attacking the C atom of CH2C12 and CHCl3 to activate a C-Cl bond;2) Both reaction systems were carried out via triplet reaction channels;3) CH2=TiCl2 has singlet and triplet isomers,and the singlet one is more stable;4) The HOMO of CH2=TiCl2（S） illustrates a π-bonding interaction between C and Ti;5) Only singlet HC÷TiCl3 was located,and the Mulliken atomic spin densities show that the two single electrons are mostly on the C atom.