Zn-N<sub>x</sub> sites on N-doped carbon for aerobic oxidative cleavage and esterification of C(CO)-C bonds.

Xie, Chao; Lin, Longfei; Huang, Liang; Wang, Zixin; Jiang, Zhiwei; Zhang, Zehui; Han, Buxing · Nat Commun · 2021

basic_science · Level V

Where this comes from

Abstract

Selective cleavage of C-C bonds is very important in organic chemistry, but remains challenging because of their inert chemical nature. Herein, we report that Zn/NC-X catalysts, in which Zn<sup>2+</sup> coordinate with N species on microporous N-doped carbon (NC) and X denotes the pyrolysis temperature, can effectively catalyze aerobic oxidative cleavage of C(CO)-C bonds and quantitatively convert acetophenone to methyl benzoate with a yield of 99% at 100 °C. The Zn/NC-950 can be applied for a wide scope of acetophenone derivatives as well as more challenging alkyl ketones. Detail mechanistic investigations reveal that the catalytic performance of Zn/NC-950 can be attributed to the coordination between Zn<sup>2+</sup> and N species to change the electronic state of the metal, synergetic effect of the Zn single sites with their surrounding N atoms, as well as the microporous structure with the high surface area and structural defects of the NC.