Boron based intramolecular heterocyclic frustrated Lewis pairs as organocatalysts for CO₂ adsorption and activation

Abstract

The massive increase in the amount of carbon dioxide (CO 2 ) in the atmosphere has led to serious environmental problems. One of the best ways to tackle this problem is the CO 2 capture and its utilization as a C1 carbon source for the production of industrially valuable chemicals. But the thermodynamic stability of the CO 2 molecule poses a great challenge in its transformation. Since the last two decades, various metal-based and organic catalysts have been developed for the adsorption and activation of CO 2 . Among all the catalysts the Frustrated Lewis pairs (FLPs) have been shown great potential in CO 2 capture and conversion. Thus, in the present work, Intramolecular Frustrated Lewis pairs (IFLP) based on N-Heterocycles with boron group functionalization at the α-position to N has been theoretically investigated for CO 2 activation. Thorough orbital analysis has been carried out to investigate the reactivity of the proposed catalytic systems. The result shows that the considered IFLPs are capable of activating CO 2 with minimum energy requirements. The CO 2 activation energy range between 8 and 14 kcal/mol. The non-polar solvent was found to be the suitable medium for the reaction. Also, the reversibility of the adducts formed with the IFLPs can be controlled by appropriate substitution at B atom in the IFLPs.atoms in molecule (AIM) theory, density functional theory (DFT), frustrated Lewis pairs (FLP), intramolecular frustrated Lewis pairs (IFLP), natural bond orbitals (NBO)

Novel Insight into the Molecular Frustration of IFLPs Based on Boron-Functionalized Pyrimidines for CO2 Sequestration

“…It signifies the application of the presented IFLPs as organocatalysts for CO 2 conversion into valuable chemicals. The present work showcases a whole new range of N/B IFLPs based on pyrimidine, which may show better properties than previously reported heterocyclic N/B IFLPs . The considered IFLPs can be used to functionalize metal–organic frameworks for catalytic reduction of CO 2 as suggested by Ye and Johnson or can be supported over silica nanopowder for the same.…”

“…The present work showcases a whole new range of N/B IFLPs based on pyrimidine, which may show better properties than previously reported heterocyclic N/B IFLPs. 70 The considered IFLPs can be used to functionalize metal−organic frameworks for catalytic reduction of CO 2 as suggested by Ye and Johnson 71 or can be supported over silica nanopowder 72 for the same. The pyrimidine-based IFLPs may have a wider range of applications in terms of CO 2 capture and conversion.…”

“…The pioneering work by Stephan and co-workers on frustrated Lewis pairs (FLPs) has created new portals in the field of CO 2 activation. − Since then, for the activation and conversion of CO 2 , various FLPs based on boron/aluminum, boron/nitrogen, and boron/phosphorus have been investigated. − Among the FLPs, the intramolecular frustrated Lewis pairs (IFLPs) are the most interesting ones. To date, various IFLPs have been explored theoretically, − still there is a lot of room for new and simple N/B-based IFLPs. Thus, in the present work, an attempt has been made to computationally investigate the IFLPs based on boron-functionalized pyrimidine for the activation and capture of CO 2 .…”

Alanine boronic acid functionalized UiO‐66 MOF as a nanoreactor for the conversion of CO2 into formic acid

“…[29][30][31][32] Since the first appearance of FLPs, various FLPs have been developed and investigated for CO 2 sequestration. [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51] Recently, Jiang and co-workers investigated Phosphorus/Boron based bridged FLPs for CO 2 hydrogenation and found them to be a potential catalyst. 52 In addition to the molecular catalysts, reactions inside molecular confinements have also been considered as a powerful tool in accelerating the reaction.…”

“…Thus, the quest for developing a better and metal‐free catalyst for CO 2 reduction is going on, 18–28 and the emergence of Frustrated Lewis pairs (FLPs) has created a whole new dimension in this area 29–32 . Since the first appearance of FLPs, various FLPs have been developed and investigated for CO 2 sequestration 33–51 . Recently, Jiang and co‐workers investigated Phosphorus/Boron based bridged FLPs for CO 2 hydrogenation and found them to be a potential catalyst 52 …”