Homogeneous Catalytic CO2 Hydrogenation by [Fe]-Hydrogenase Bioinspired Complexes: A Computational Study

Author(s)

Ramos, Vania M. ; de Oliveira-Filho, Antonio G. S. ; de Lima Batista, Ana Paula

• Document type: Journal article
• Source: Journal of Physical Chemistry A; v. 126, n. 13, p. 9-pg., 2022-04-07.

Abstract

Computational modeling at the DLPNO-CCSD(T)/CBS//M06-L/def2-TZVP level of theory was used to propose four different iron catalysts whose structures were inspired on the ylidene) pyridine)). Through these electronic structure calculations, the catalytic mechanism of the reaction was explored. The intermediates and transition states present along the reaction coordinate were identified and described as to their equilibrium geometries, vibrational frequencies, and energies. Quasi-harmonic corrections were performed considering conditions analogous to those used experimentally. To compare the catalytic activities of the studied catalysts, turnover frequencies (TOFs) were calculated. Based on the explored catalytic cycles and TOF values (D(1) > C(1) > D(2) > C(2)), the most suitable iron catalysts are those with tridentate phosphine pincer-type ligands coordinated to the metal center. These systems are new promising iron catalysts to promote the CO2 hydrogenation to formic acid without any use of bases or additives. (AU)

• FAPESP's process: 15/22203-6 - N-Heterocyclic Carbene Based Compounds in CO2 Activation: A Computational Approach
• Grantee: Ana Paula de Lima Batista
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 20/08553-2 - Computational spectroscopy of diatomic molecules
• Grantee: Antonio Gustavo Sampaio de Oliveira Filho
• Support Opportunities: Regular Research Grants
• FAPESP's process: 15/11714-0 - Reactivity, transformation, fixation, and spectroscopy of systems involving CO2
• Grantee: Antonio Gustavo Sampaio de Oliveira Filho
• Support Opportunities: Regular Research Grants