A DFT study on the mechanisms of hydrogenation and hydrosilylation of nitrous oxide catalyzed by a ruthenium PNP pincer complex

作者：Yao, Lanying; Li, Yang; Huang, Lvtao; Guo, Kai; Ren, Gerui; Wu, Zunyi^*; Lei, Qunfang; Fang, Wenjun; Xie, Hujun^*

来源：Computational and Theoretical Chemistry, 2018, 1128: 48-55.

DOI：10.1016/j.comptc.2018.02.010

• DFT calculations
• Nitrous oxide
• Ruthenium complex
• Reaction mechanism
• Hydrogenation
• Hydrosilylation

The mechanisms of hydrogenation and hydrosilylation of nitrous oxide catalyzed by a ruthenium PNP pincer complex I have been studied through quantum chemistry calculations at the M06 level of theory. It was found that the catalytic cycle of hydrogenation of nitrous oxide contains three steps, hydrogenation of the dearomatized PNP pincer complex 1, mono oxygen transfer and water release. In addition, the catalytic cycle of hydrosilylation of nitrous oxide also includes three steps, hydrosilylation of the dearomatized PNP pincer complex 1, mono oxygen transfer, dehydrogenative coupling of silanol and silane/direct Si-O bond coupling. The calculations suggested that the water molecule play an important role to lower the barrier for N-2 liberation. Frontier molecular orbital theory and NBO analysis indicated that nitrous oxide is activated by hydrido ligand via nucleophilical attacking. Present calculations are in good agreement with the experimental observations and can help to understand the activation of N2O.

• 出版日期2018-3-15
• 单位浙江大学; 浙江工商大学