Affiliation:
1. State Key Laboratory of Chemical Resource Engineering Institute of Computational Chemistry College of Chemistry Beijing University of Chemical Technology BeiSanHuan East Rd 15th Beijing 100029 China
2. State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry College of Chemistry and Chemical Engineering Xiamen University Xiamen 361005 China
Abstract
AbstractIn this paper the density functional theory (DFT) method was employed to investigate the cross‐coupling of methanol with benzyl alcohol to afford methyl benzoate, catalysed by Mn‐PNN pincer complex. The whole reaction process mainly includes three stages: the dehydrogenation of benzyl alcohol to benzaldehyde, the coupling of benzaldehyde with methanol to hemiacetal and the dehydrogenation of hemiacetal to methyl benzoate. The calculated results indicated that two dehydrogenation processes are influenced by two competitive mechanisms of inner and outer spheres. Dehydrogenation of benzyl alcohol to benzaldehyde is the rate‐determining step of the whole reaction, with the energy barrier of 22.1 kcal/mol. In addition, the regeneration of catalyst is also extremely important. Compared with direct dehydrogenation, the dehydrogenation mode assisted by formic acid is more advantageous. This work might provide theoretical insights and shed light on the design of cheap transition‐metal catalysts for the dehydrogenation reaction.
Funder
National Natural Science Foundation of China
Subject
General Chemistry,Catalysis,Organic Chemistry