Mechanism of TBD-catalyzed hydrolysis of acetonitrile |
| |
Authors: | Jun Ma Xuelan Zhang Ning Zhao Fukui Xiao Wei Wei Yuhan Sun |
| |
Affiliation: | aState Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, PR China;bGraduate University of The Chinese Academy of Sciences, Beijing 100049, PR China |
| |
Abstract: | 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) has recently been shown to be an effective organocatalyst for the hydrolysis reaction of acetonitrile. This reaction involves the acetamide-forming reaction of acetonitrile hydrolysis and the further hydrolysis of acetamide to form acetic acid and NH3. Density functional theory (DFT) and Hartree–Fock (HF) methods were employed to comprehensively investigate these two hydrolysis steps to elucidate the TBD-catalyzation mechanism. Structures and energies of the reactants, intermediates, transition states and products along the reaction path were presented. Charge population and bond orders were given by natural bond orbital (NBO) analysis to clarify the computed atomic and molecular behaviors. The results showed that compared with the noncatalyzed reaction, the TBD-catalyzed process had significantly lower energy barriers in both the hydration steps and the isomerization steps. As a result, the whole reaction process could be accelerated and the TBD-catalyzation mechanism was clarified. |
| |
Keywords: | Catalysis mechanism TBD Acetonitrile hydrolysis DFT NBO |
本文献已被 ScienceDirect 等数据库收录! |
|