Unravelling Enzymatic Features in a Supramolecular Iridium Catalyst by Computational Calculations - Université de Rennes Access content directly
Journal Articles Chemistry - A European Journal Year : 2022

Unravelling Enzymatic Features in a Supramolecular Iridium Catalyst by Computational Calculations

Abstract

Non-biological catalysts following the governing principles of enzymes are attractive systems to disclose unprecedented reactivities. Most of those existing catalysts feature an adaptable molecular recognition site for substrate binding that are prone to undergo conformational selection pathways. Herein, we present a non-biological catalyst able to bind substrates via the induced fit model according to in-depth computational calculations. The system, which is constituted by an inflexible substrate-recognition site derived from a zinc-porphyrin in the second coordination sphere, features destabilization of ground states as well as stabilization of transition states for the relevant iridium-catalyzed C-H bond borylation of pyridine. In addition, this catalyst appears to be most suited to tightly bind the transition state rather than the substrate. Besides these features, which are reminiscent from the action mode of enzymes, new elementary catalytic steps (i.e. C-B bond formation and catalyst regeneration) have been disclosed owing to the unique distortions encountered in the different intermediates and transition states.
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Dates and versions

hal-03713897 , version 1 (05-07-2022)

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Michele Tomasini, Lucia Caporaso, Jonathan Trouvé, Jordi Poater Teixidor, Rafael Gramage-Doria, et al.. Unravelling Enzymatic Features in a Supramolecular Iridium Catalyst by Computational Calculations. Chemistry - A European Journal, 2022, 28 (57), ⟨10.1002/chem.202201970⟩. ⟨hal-03713897⟩
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