Mechanism and dynamic correlation effects in cycloaddition reactions of singlet difluorocarbene to alkenes and disilene.

Abstract

Mechanisms of the cycloaddition reactions of singlet difluorocarbene (CF(2)) to alkenes and disilene were studied using CASSCF, MR-MP2, CR-CC(2,3), and UB3LYP methods in combination with basis sets up to 6-311++G(3d,p). The CASSCF(4,4) energies suggest that the cycloadditions all follow the stepwise mechanism. However, energies calculated using the MR-MP2(4,4) and CR-CC(2,3) methods in combination with the 6-311G(d) or larger basis sets consistently show that the reactions follow a concerted mechanism. The stepwise mechanisms predicted at the CASSCF level are "artificial" because of their neglect of dynamic electron correlation effects. The importance of dynamic electron correlation in determining the mechanistic nature of the reactions is explained through knowledge of the reacting system's geometries and charges along the reaction path.

DOI: 10.1021/jp901553y

Cite this paper

@article{Gao2009MechanismAD, title={Mechanism and dynamic correlation effects in cycloaddition reactions of singlet difluorocarbene to alkenes and disilene.}, author={Xingfa Gao and Yuhki Ohtsuka and Kazuya Ishimura and Shigeru Nagase}, journal={The journal of physical chemistry. A}, year={2009}, volume={113 36}, pages={9852-60} }