Homogeneous Catalytic CO2 Hydrogenation by [Fe]-Hydrogenase Bioinspired Complexes: A Computational Study.
J Phys Chem A
; 126(13): 2082-2090, 2022 Apr 07.
Article
em En
| MEDLINE
| ID: mdl-35345882
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 [Fe]-hydrogenase active site: [Fe(MePNNHNP)(acmp)] (C(1), MePNNHNP = 2,6-bis(dimethylphosphine), acmp = acylmethylpyridine), [Fe(CNNHNC)(acmp)] (C(2), CNNHNC = 2,6-bis(methylimidazol-2-ylidene)), [Fe(MePNNNP)(acmp)] (D(1), MePNNNP = 2,6-bis((dimethylphosphine)pyridine)), and [Fe(CNNNC)(acmp)] (D(2), CNNNC = 2,6-bis((methylimidazol-2-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.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Dióxido de Carbono
/
Materiais Biomiméticos
/
Hidrogenase
Idioma:
En
Revista:
J Phys Chem A
Assunto da revista:
QUIMICA
Ano de publicação:
2022
Tipo de documento:
Article
País de afiliação:
Brasil
País de publicação:
Estados Unidos