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Oriented (Local) Electric Fields Drive the Millionfold Enhancement of the H‐Abstraction Catalysis Observed for Synthetic Metalloenzyme Analogues
Author(s) -
Stuyver Thijs,
Ramanan Rajeev,
Mallick Dibyendu,
Shaik Sason
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201916592
Subject(s) - chemistry , catalysis , hydrogen atom abstraction , electrostatics , porphyrin , abstraction , combinatorial chemistry , hydrogen , stereochemistry , computational chemistry , photochemistry , organic chemistry , philosophy , epistemology
Abstract This contribution follows the recent remarkable catalysis observed by Groves et al. in hydrogen‐abstraction reactions by a) an oxoferryl porphyrin radical‐cation complex [Por ⋅+ Fe IV (O)L ax ] and b) a hydroxoiron porphyrazine ferric complex [PyPzFe III (OH)L ax ], both of which involve positively charged substituents on the outer circumference of the respective macrocyclic ligands. These charge‐coronated complexes are analogues of the biologically important Compound I (Cpd I) and synthetic hydroxoferric species, respectively. We demonstrate that the observed enhancement of the H‐abstraction catalysis for these systems is a purely electrostatic effect, elicited by the local charges embedded on the peripheries of the respective macrocyclic ligands. Our findings provide new insights into how electrostatics can be employed to tune the catalytic activity of metalloenzymes and can thus contribute to the future design of new and highly efficient hydrogen‐abstraction catalysts.