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Impact of Intramolecular Hydrogen Bonding on the Reactivity of Cupric Superoxide Complexes with O−H and C−H Substrates
Author(s) -
Diaz Daniel E.,
Quist David A.,
Herzog Austin E.,
Schaefer Andrew W.,
Kipouros Ioannis,
Bhadra Mayukh,
Solomon Edward I.,
Karlin Kenneth D.
Publication year - 2019
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.201908471
Subject(s) - intramolecular force , reactivity (psychology) , chemistry , superoxide , hydrogen bond , photochemistry , stereochemistry , polymer chemistry , molecule , organic chemistry , enzyme , medicine , alternative medicine , pathology
The dioxygen reactivity of a series of TMPA‐based copper(I) complexes (TMPA=tris(2‐pyridylmethyl)amine), with and without secondary‐coordination‐sphere hydrogen‐bonding moieties, was studied at −135 °C in 2‐methyltetrahydrofuran (MeTHF). Kinetic stabilization of the H‐bonded [(( X1 ) ( X2 )TMPA)Cu II (O 2 .− )] + cupric superoxide species was achieved, and they were characterized by resonance Raman (rR) spectroscopy. The structures and physical properties of [(( X1 ) ( X2 )TMPA)Cu II (N 3 − )] + azido analogues were compared, and the O 2 .− reactivity of ligand–Cu I complexes when an H‐bonding moiety is replaced by a methyl group was contrasted. A drastic enhancement in the reactivity of the cupric superoxide towards phenolic substrates as well as oxidation of substrates possessing moderate C−H bond‐dissociation energies is observed, correlating with the number and strength of the H‐bonding groups.
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