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Unravelling Enzymatic Features in a Supramolecular Iridium Catalyst by Computational Calculations
Author(s) -
Tomasini Michele,
Caporaso Lucia,
Trouvé Jonathan,
Poater Jordi,
GramageDoria Rafael,
Poater Albert
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202201970
Subject(s) - iridium , catalysis , chemistry , supramolecular chemistry , transition state , substrate (aquarium) , borylation , porphyrin , combinatorial chemistry , coordination sphere , pyridine , molecular recognition , photochemistry , molecule , organic chemistry , biology , ecology , alkyl , aryl
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 that is 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 of the action modes 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.