Cyclopentadienone Diphosphine Ruthenium Complex: A Designed Catalyst for the Hydrogenation of Carbon Dioxide to Methanol

Yanhui Tang; Min Pu; Ming Lei

doi:10.1021/acs.joc.3c02438

Cyclopentadienone Diphosphine Ruthenium Complex: A Designed Catalyst for the Hydrogenation of Carbon Dioxide to Methanol

J Org Chem. 2024 Feb 16;89(4):2431-2439. doi: 10.1021/acs.joc.3c02438. Epub 2024 Feb 2.

Authors

Yanhui Tang^{1

2}, Min Pu¹, Ming Lei¹

Affiliations

¹ State Key Laboratory of Chemical Resource Engineering, Institute of Computational Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, P.R. China.
² School of Materials Design and Engineering, Beijing Institute of Fashion Technology, Beijing 100029, P.R. China.

PMID: 38306607
DOI: 10.1021/acs.joc.3c02438

Abstract

The development of homogeneous metal catalysts for the efficient hydrogenation of carbon dioxide (CO₂) into methanol (CH₃OH) remains a significant challenge. In this study, a new cyclopentadienone diphosphine ligand (CPDDP ligand) was designed, which could coordinate with ruthenium to form a Ru-CPDDP complex to efficiently catalyze the CO₂-to-methanol process using dihydrogen (H₂) as the hydrogen resource based on density functional theory (DFT) mechanistic investigation. This process consists of three catalytic cycles, stage I (the hydrogenation of CO₂ to HCOOH), stage II (the hydrogenation of HCOOH to HCHO), and stage III (the hydrogenation of HCHO to CH₃OH). The calculated free energy barriers for the hydrogen transfer (HT) steps of stage I, stage II, and stage III are 7.5, 14.5, and 3.5 kcal/mol, respectively. The most favorable pathway of the dihydrogen activation (DA) steps of three stages to regenerate catalytic species is proposed to be the formate-assisted DA step with a free energy barrier of 10.4 kcal/mol. The calculated results indicate that the designed Ru-CPDDP and Ru-CPDDPEt complexes could catalyze hydrogenation of CO₂ to CH₃OH (HCM) under mild conditions and that the transition-metal owning designed CPDDP ligand framework be one kind of promising potential efficient catalysts for HCM.