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Updated: Aug 9, 2025
Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
Published on: November 9, 2019
Mechanism of Hydroboration of CO2 Using an Fe Catalyst: What Controls the Reactivity and Product Selectivity?
Asmita Sen1, Mursaleem Ansari1, Gopalan Rajaraman1
1Department of Chemistry, IIT Bombay, Powai 400076, Maharashtra, India.
Abstract:
Using a combination of density functional theory (DFT) and ab initio complete active space self-consistent field (CASSCF) calculations, various elementary steps in the mechanism of the reductive hydroboration of CO2 to two-electron-reduced boryl formate, four-electron-reduced bis(boryl)acetal, and six-electron-reduced methoxy borane by the [Fe(H)2(dmpe)2] catalyst were established. The replacement of hydride by oxygen ligation after the boryl formate insertion step is the rate-determining step. Our work unveils, for the first time, (i) how a substrate steers product selectivity in this reaction and (ii) the importance of configurational mixing in contracting the kinetic barrier heights. Based on the reaction mechanism established, we have further focused on the effect of other metals, such as Mn and Co, on rate-determining steps and on catalyst regeneration.
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