Design of CO2 hydrogenation catalysts based on phosphane/borane frustrated Lewis pairs and xanthene-derived scaffolds

• Published in: Catalysis communications Vol. 162; p. 106385
• Main Authors: Delarmelina, Maicon, Carneiro, José Walkimar de M., Catlow, C. Richard A., Bühl, Michael
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.02.2022; Elsevier
• Subjects: CO2 hydrogenation; DFT; Formic acid; Frustrated Lewis pair; Xanthene; DFT; Frustrated Lewis pair; Formic acid; CO2 hydrogenation; Xanthene
• ISSN: 1566-7367; 1873-3905
• DOI: 10.1016/j.catcom.2021.106385

New naphtho[2,1,8,7-klmn]xanthene and benzo[kl]xanthene-based intramolecular phosphane–borane frustrated Lewis pairs (FLPs) were investigated in catalyzed H2 activation and CO2 hydrogenation processes. According to DFT predictions at the B3LYP-D3 level, the presence of rigid scaffolds and increased P···B distances in the investigated FLPs lead to a remarkable drop in the energy barrier for CO2 hydrogenation (by up to 19.2 kcal mol−1, compared to the parent dimethylxanthene-based FLP). Furthermore, the energy differences between the transition states for H2 activation and CO2 hydrogenation are significantly reduced, making both processes feasible under relatively mild experimental conditions. [Display omitted] •Rigid scaffolds in FLPs lead to drop in the energy barrier for CO2 hydrogenation•H2 activation and CO2 hydrogenation are feasible under mild conditions•New examples of xanthene-inspired intramolecular P/B FLPs•Potential role of FLPs in dehydrogenation of formic acid