Evidence of Oxygen Activation in the Reaction between an N-Heterocyclic Carbene and M3N@Ih(7)-C80: An Unexpected Method of Steric Hindrance Release

Muqing Chen; Wangqiang Shen; Ping Peng; Lipiao Bao; Shasha Zhao; Yunpeng Xie; Peng Jin; Hongyun Fang; Fang-Fang Li; Xing Lu

doi:10.1021/acs.joc.6b03004

Evidence of Oxygen Activation in the Reaction between an N-Heterocyclic Carbene and M₃N@I_h(7)-C₈₀: An Unexpected Method of Steric Hindrance Release

J Org Chem. 2017 Apr 7;82(7):3500-3505. doi: 10.1021/acs.joc.6b03004. Epub 2017 Mar 13.

Authors

Muqing Chen^{1

2}, Wangqiang Shen², Ping Peng², Lipiao Bao², Shasha Zhao², Yunpeng Xie², Peng Jin³, Hongyun Fang², Fang-Fang Li², Xing Lu²

Affiliations

¹ Department of Materials Physics, School of Physics and Mechanical& Electronical Engineering, Hubei University of Education 129 Gaoxin Second Road, Wuhan Hi-Tech Zone, Wuhan 430205, P.R. China.
² State Key Laboratory of Materials Processing and Die & Mold Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology , 1037 Luoyu Road, Wuhan 430074, P.R. China.
³ School of Materials Science and Engineering, Hebei University of Technology , Tianjin 300130, P. R. China.

PMID: 28271713
DOI: 10.1021/acs.joc.6b03004

Abstract

We herein demonstrate for the first time the unexpected oxygen-involving reaction between M₃N@I_h(7)-C₈₀ (M = Sc, Lu) and 1,3-bis(diisopropylphenyl)imidazol-2-ylene (1). By introducing a tiny amount of oxygen into the reaction, unprecedented products (2a for Sc₃N@C₈₀ and 3a for Lu₃N@C₈₀) with the normal carbene center C2 singly bonded to a triple hexagonal junction (THJ) cage carbon together with an oxygen atom bridging the same THJ carbon atom and a neighboring carbon atom forming an epoxy structure are obtained. In situ mechanism study, in combination with theoretical calculations, reveals that the bond-breaking peroxidation facilitates the formation of the unexpected products 2a and 3a, providing new insight into fullerene chemistry.

Publication types

Research Support, Non-U.S. Gov't