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The reaction mechanisms of Ti(~3F) + CH_2C1_2→CH_2=TiCl_2 and Ti(~3F) + CHC1_3→HC÷TiCl_3 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 CH_2C1_2 and CHCl_3 to activate a C-Cl bond;2) Both reaction systems were carried out via triplet reaction channels;3) CH_2=TiCl_2 has singlet and triplet isomers,and the singlet one is more stable;4) The HOMO of CH_2=TiCl_2(S) illustrates a π-bonding interaction between C and Ti;5) Only singlet HC÷TiCl_3 was located,and the Mulliken atomic spin densities show that the two single electrons are mostly on the C atom.
The reaction mechanisms of Ti (~ 3F) + CH_2C1_2 → CH_2 = TiCl_2 and Ti (~ 3F) + CHCl_3 → HC ÷ TiCl_3 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 were initiated by Ti (~ 3F) atom attacking the C atom of CH_2C1_2 and CHCl_3 to activate a C-Cl bond; 2) Both reaction systems were carried out via triplet reaction channels; 3) CH_2 = TiCl_2 has singlet and triplet isomers, and the singlet one is more stable; 4) The HOMO of CH_2 = TiCl_2 (S) illustrates a π-bonding interaction between C and Ti; 5) Only singlet HC ÷ TiCl_3 was located , and the Mulliken atomic spin densities show that the two single electrons are mostly on the C atom.