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Theory-guided development of homogeneous catalysts for the reduction of CO₂ to formate, formaldehyde, and methanol derivatives.

ABSTRACT: The stepwise catalytic reduction of carbon dioxide (CO₂) to formic acid, formaldehyde, and methanol opens non-fossil pathways to important platform chemicals. The present article aims at identifying molecular control parameters to steer the selectivity to the three distinct reduction levels using organometallic catalysts of earth-abundant first-row metals. A linear scaling relationship was developed to map the intrinsic reactivity of 3d transition metal pincer complexes to their activity and selectivity in CO₂ hydrosilylation. The hydride affinity of the catalysts was used as a descriptor to predict activity/selectivity trends in a composite volcano picture, and the outstanding properties of cobalt complexes bearing bis(phosphino)triazine PNP-type pincer ligands to reach the three reduction levels selectively under different reaction conditions could thus be rationalized. The implications of the composite volcano picture were successfully experimentally validated with selected catalysts, and the challenging intermediate level of formaldehyde could be accessed in over 80% yield with the cobalt complex 6. The results underpin the potential of tandem computational-experimental approaches to propel catalyst design for CO₂-based chemical transformations.

SUBMITTER: Cramer HH

PROVIDER: S-EPMC10016328 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature

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Theory-guided development of homogeneous catalysts for the reduction of CO<sub>2</sub> to formate, formaldehyde, and methanol derivatives.

Cramer Hanna H HH Das Shubhajit S Wodrich Matthew D MD Corminboeuf Clémence C Werlé Christophe C Leitner Walter W

Chemical science 20230209 11

The stepwise catalytic reduction of carbon dioxide (CO<sub>2</sub>) to formic acid, formaldehyde, and methanol opens non-fossil pathways to important platform chemicals. The present article aims at identifying molecular control parameters to steer the selectivity to the three distinct reduction levels using organometallic catalysts of earth-abundant first-row metals. A linear scaling relationship was developed to map the intrinsic reactivity of 3d transition metal pincer complexes to their activ ...[more]

PMID: 36937594

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Project description:To facilitate computational investigation of intermolecular interactions in the solution phase, we report the development of ALMO-EDA(solv), a scheme that allows the application of continuum solvent models within the framework of energy decomposition analysis (EDA) based on absolutely localized molecular orbitals (ALMOs). In this scheme, all the quantum mechanical states involved in the variational EDA procedure are computed with the presence of solvent environment so that solvation effects are incorporated in the evaluation of all its energy components. After validation on several model complexes, we employ ALMO-EDA(solv) to investigate substituent effects on two classes of complexes that are related to molecular CO2 reduction catalysis. For [FeTPP(CO2-κC)]2- (TPP = tetraphenylporphyrin), we reveal that two ortho substituents which yield most favorable CO2 binding, -N(CH3)3 + (TMA) and -OH, stabilize the complex via through-structure and through-space mechanisms, respectively. The coulombic interaction between the positively charged TMA group and activated CO2 is found to be largely attenuated by the polar solvent. Furthermore, we also provide computational support for the design strategy of utilizing bulky, flexible ligands to stabilize activated CO2 via long-range Coulomb interactions, which creates biomimetic solvent-inaccessible "pockets" in that electrostatics is unscreened. For the reactant and product complexes associated with the electron transfer from the p-terphenyl radical anion to CO2, we demonstrate that the double terminal substitution of p-terphenyl by electron-withdrawing groups considerably strengthens the binding in the product state while moderately weakens that in the reactant state, which are both dominated by the substituent tuning of the electrostatics component. These applications illustrate that this new extension of ALMO-EDA provides a valuable means to unravel the nature of intermolecular interactions and quantify their impacts on chemical reactivity in solution.

Dataset Information

Theory-guided development of homogeneous catalysts for the reduction of CO₂ to formate, formaldehyde, and methanol derivatives.

Publications

Theory-guided development of homogeneous catalysts for the reduction of CO<sub>2</sub> to formate, formaldehyde, and methanol derivatives.

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Theory-guided development of homogeneous catalysts for the reduction of CO2 to formate, formaldehyde, and methanol derivatives.

Publications

Theory-guided development of homogeneous catalysts for the reduction of CO<sub>2</sub> to formate, formaldehyde, and methanol derivatives.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Theory-guided development of homogeneous catalysts for the reduction of CO₂ to formate, formaldehyde, and methanol derivatives.