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Issue 3, 2016
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Sc3N@Ih-C80 as a novel Lewis acid to trap abnormal N-heterocyclic carbenes: the unprecedented formation of a singly bonded [6,6,6]-adduct

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Abstract

The reaction between an N-heterocyclic carbene (NHC), namely 1,3-bis(diisopropylphenyl)-imidazol-2-ylene (1), and Sc3N@Ih-C80 successfully affords a Lewis acid–base pair (2a). Single crystal X-ray crystallographic results unambiguously reveal the unexpected structure of 2a where the abnormal carbene center of the NHC is connected to a triple-hexagon-junction (THJ) carbon atom of Sc3N@Ih-C80via a single bond. Theoretical calculations reveal that selective entrapment of the abnormal carbene 1 is caused by the steric hindrance between the normal NHC moiety and the fullerene cage, which precludes the formation of normal carbene adducts. Furthermore, the analysis of the electronic density distribution on the cage of Sc3N@Ih-C80 indicates that THJ carbons bear relatively low negative charge densities and, accordingly, are easily attacked by the electron-rich NHC 1 to form the singly bonded [6,6,6]-adduct 2a instead of the corresponding [5,6,6]-adduct 2b. It is thus confirmed that the regioselective formation of 2a is a synergistic effect of both cage size and electron density distribution. Sc3N@Ih-C80, although with a highly charged cage, is proven to show excellent Lewis acidity, opening a wide avenue toward carbon-based Lewis acids taking into account the diversity of endohedral metallofullerenes.

Graphical abstract: Sc3N@Ih-C80 as a novel Lewis acid to trap abnormal N-heterocyclic carbenes: the unprecedented formation of a singly bonded [6,6,6]-adduct

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Article information


Submitted
27 Oct 2015
Accepted
01 Dec 2015
First published
02 Dec 2015

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2016,7, 2331-2334
Article type
Edge Article
Author version available

Sc3N@Ih-C80 as a novel Lewis acid to trap abnormal N-heterocyclic carbenes: the unprecedented formation of a singly bonded [6,6,6]-adduct

M. Chen, L. Bao, M. Ai, W. Shen and X. Lu, Chem. Sci., 2016, 7, 2331
DOI: 10.1039/C5SC04070A

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