Activation of Small Molecules and Hydrogenation of CO2 Catalyzed by Frustrated Lewis Pairs

Manas Ghara,Ranita Pal,Pratim Kumar Chattaraj

doi:10.3390/catal12020201

Abstract

The chemistry of frustrated Lewis pair (FLP) is widely explored in the activation of small molecules, the hydrogenation of CO2, and unsaturated organic species. A survey of several experimental works on the activation of small molecules by FLPs and the related mechanistic insights into their reactivity from electronic structure theory calculation are provided in the present review, along with the catalytic hydrogenation of CO2. The mechanistic insight into H2 activation is thoroughly discussed, which may provide a guideline to design more efficient FLP for H2 activation. FLPs can activate other small molecules like, CO, NO, CO2, SO2, N2O, alkenes, alkynes, etc. by cooperative action of the Lewis centers of FLPs, as revealed by several computational analyses. The activation barrier of H2 and other small molecules by the FLP can be decreased by utilizing the aromaticity criterion in the FLP as demonstrated by the nucleus independent chemical shift (NICS) analysis. The term boron-ligand cooperation (BLC), which is analogous to the metal-ligand cooperation (MLC), is invoked to describe a distinct class of reactivity of some specific FLPs towards H2 activation.

Highlights

Academic Editor: Luca GonsalviThe application of catalysts in expediting the rate of chemical reactions has very high industrial importance
In a study performed by our group [41], we have explored the influence of boronIn a study performed by our group [41], we have explored the influence of boronligand cooperation (BLC) in H2 activation and the associated effects on the corresponding ligand cooperation (BLC) in H2 activation and the associated effects on the corresponding activation barrier
In a study performed by our group [41], we have explored the influence of boronligand cooperation (BLC) in H2 activation and the associated effects on the corresponding activation barrier

Summary

Introduction

The application of catalysts in expediting the rate of chemical reactions has very high industrial importance. Germylene [10], [10], stanylene [11], and higher analogs acetylene, such as ArGeGeAr [12] Another class of promising known as the pair pair (FLP), Another class ofidea promising catalysts, known asacid the frustrated. Introduced based on the idea that a pair of bulky carbene such as silylene [9], germylene [10], stanylene [11], and higher analogs of acetylene, introduced based on the idea that a pair of bulky cannot form adduct due to steric repulsion. An alternative reaction channel is opened as a reported as non-linked known as includes, intermolecular. The LB component includes various amines, both as non-linked ( known as intermolecular and linked (intramolecular FLP). Structures some and intramolecular along with important roles,and others [15,16,17,18,19,20,21,22,23]

FLPs activation bymetal-free

H22 Cleavage

Cleavage

Catalytic Hydrogenation by FLPs

OH by insertion of CO2 into

Activation of article

Activation of Other Small Molecules

Some examples of small molecule activation byby

Summary