title: Dehydrogenation of benzyl alcohol with N2O as the hydrogen acceptor catalyzed by the rhodium(i) carbene complex: insights from quantum chemistry calculations.
abstract: The detailed mechanisms of the dehydrogenation of benzyl alcohol with N2O as the hydrogen acceptor catalyzed by the rhodium(i) carbene complex for the formation of the corresponding carboxylic acid or ester have been investigated via density functional theory (DFT) calculations at the M06 level of theory. Three cycles were considered for the formation of benzaldehyde, benzyl benzoate and benzoic acid. On the basis of the calculations, the rate-determining step for these three cycles is involved in N2O activation by the rhodium ammine hydride complex with an activation barrier of only 22.6 kcal mol-1, which is different from the previous mechanism proposed by Gianetti and co-workers, where the hydride is transferred from the Rh atom to the oxygen atom of N2O with a barrier of 30.5 kcal mol-1. In addition, the calculations also demonstrated that one more N2O is necessary to give benzoic acid, and the reaction can only take place under anhydrous conditions. Present calculations are in good agreement with the experimental observations and provide new insights into the dehydrogenation of benzyl alcohol with N2O as the hydrogen acceptor.
authors.affiliation: Department of Applied Chemistry, Zhejiang Gongshang University, Hangzhou 310018, People's Republic of China. hujunxie@gmail.com.
authors.forename: Hujun
authors.initials: H
authors.lastname: Xie
authors.affiliation: Department of Applied Chemistry, Zhejiang Gongshang University, Hangzhou 310018, People's Republic of China. hujunxie@gmail.com.
authors.forename: Yang
authors.initials: Y
authors.lastname: Li
authors.affiliation: Department of Applied Chemistry, Zhejiang Gongshang University, Hangzhou 310018, People's Republic of China. hujunxie@gmail.com.
authors.forename: Lvtao
authors.initials: L
authors.lastname: Huang
authors.affiliation: Department of Applied Chemistry, Zhejiang Gongshang University, Hangzhou 310018, People's Republic of China. hujunxie@gmail.com.
authors.forename: Fangli
authors.initials: F
authors.lastname: Nong
authors.affiliation: Department of Applied Chemistry, Zhejiang Gongshang University, Hangzhou 310018, People's Republic of China. hujunxie@gmail.com.
authors.forename: Gerui
authors.initials: G
authors.lastname: Ren
authors.affiliation: Division of Theoretical Chemistry and Biology, School of Biotechnology, KTH Royal Institute of Technology, SE-10044 Stockholm, Sweden. tingf@kth.se.
authors.forename: Ting
authors.initials: T
authors.lastname: Fan
authors.affiliation: Department of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China.
authors.forename: Qunfang
authors.initials: Q
authors.lastname: Lei
authors.affiliation: Department of Chemistry, Zhejiang University, Hangzhou 310027, People's Republic of China.
authors.forename: Wenjun
authors.initials: W
authors.lastname: Fang