A theoretical view on CrO2+-mediated C-H bond activation in ethane

作者：Tong, YongChun; Zhang, XiaoYong; Wang, QingYun^*; Xu, XinJian; Wang, YongCheng

来源：Journal of Molecular Structure, 2015, 1089: 129-134.

DOI：10.1016/j.molstruc.2015.02.046

• CrO2
• C2H6
• Minimum energy crossing point (MECP)
• Spin-orbit coupling (SOC)
• Intersystem crossing (ISC)

The gas-phase reaction of C-H bond activation in ethane by CrO2+ has been investigated using density functional theory (DFT) at the UB3LYP/6-311G(2d,p) level. Our results reveal that the activation process is actually a spin-forbidden reaction. The involved crossing point between the doublet and quartet potential energy surfaces (PES) has been discussed by two well-known methods, i.e., intrinsic reaction coordinate (IRC) approach for crossing point (CP) and Harvey's algorithm for minimum energy crossing point (MECP). The obtained single (p(1)(ISC) = 2.48 x 10(-3)) and double (P-1(ISC) = 4.95 x 10(-3)) passes estimated at MECP show that the intersystem crossing (ISC) occurs with a little probability. The C-H bond activation processes should proceed to be endothermic by 73.16 kJ/mol on the doublet surface without any spin change.

• 出版日期2015-6-5
• 单位西北师范大学; 河西学院; 吉林大学