Systematic Assessment of the Catalytic Reactivity of Frustrated Lewis Pairs in C-H Bond Activation

Author:

Guo Yongjie1,Lian Xueqi2,Zhang Hao1,Zhang Xueling2,Chen Jun1,Chen Changzhong1,Lan Xiaobing1ORCID,Shao Youxiang2

Affiliation:

1. Hunan Provincial Key Laboratory of Xiangnan Rare-Precious Metals Compounds Research and Application, School of Chemistry and Environmental Science, Xiangnan University, Chenzhou 423000, China

2. Key Laboratory of Electronic Functional Materials and Devices of Guangdong Province, School of Chemistry and Materials Engineering, Huizhou University, Huizhou 516007, China

Abstract

Unreactive C-H bond activation is a new horizon for frustrated Lewis pair (FLP) chemistry. This study provides a systematic assessment of the catalytic reactivity of recently reported intra-molecular FLPs on the activation of typical inert C-H bonds, including 1-methylpyrrole, methane, benzyl, propylene, and benzene, in terms of density functional theory (DFT) calculations. The reactivity of FLPs is evaluated according to the calculated reaction thermodynamic and energy barriers of C-H bond activation processes in the framework of concerted C-H activation mechanisms. As for 1-methylpyrrole, 14 types of N-B-based and 15 types of P-B-based FLPs are proposed to be active. Although none of the evaluated FLPs are able to catalyze the C-H activation of methane, benzyl, or propylene, four types of N-B-based FLPs are suggested to be capable of catalyzing the activation of benzene. Moreover, the influence of the strength of Lewis acid (LA) and Lewis base (LB), and the differences between the influences of LA and LB on the catalytic reactivity of FLPs, are also discussed briefly. This systematic assessment of the catalytic activity of FLPs should provide valuable guidelines to aid the development of efficient FLP-based metal-free catalysts for C-H bond activation.

Funder

The Hunan Provincial Natural Science Foundation of China

Publisher

MDPI AG

Subject

Chemistry (miscellaneous),Analytical Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Molecular Medicine,Drug Discovery,Pharmaceutical Science

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