TY - JOUR
T1 - Oriented (Local) Electric Fields Drive the Millionfold Enhancement of the H-Abstraction Catalysis Observed for Synthetic Metalloenzyme Analogues
AU - Stuyver, Thijs
AU - Ramanan, Rajeev
AU - Mallick, Dibyendu
AU - Shaik, Sason
N1 - Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2020/5/11
Y1 - 2020/5/11
N2 - 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⋅+FeIV(O)Lax] and b) a hydroxoiron porphyrazine ferric complex [PyPzFeIII(OH)Lax], 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.
AB - 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⋅+FeIV(O)Lax] and b) a hydroxoiron porphyrazine ferric complex [PyPzFeIII(OH)Lax], 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.
KW - Cpd I
KW - electrostatic catalysis
KW - local electric fields
KW - metalloenzymes
KW - oriented external electric fields
UR - http://www.scopus.com/inward/record.url?scp=85081948117&partnerID=8YFLogxK
U2 - 10.1002/anie.201916592
DO - 10.1002/anie.201916592
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C2 - 32097514
AN - SCOPUS:85081948117
SN - 1433-7851
VL - 59
SP - 7915
EP - 7920
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 20
ER -