Impact of Intramolecular Hydrogen Bonding on the Reactivity of Cupric Superoxide Complexes with O−H and C−H Substrates

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)CuII(O2....

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Published in:Angewandte Chemie 2019-12, Vol.131 (49), p.17736-17740
Main Authors: Diaz, Daniel E., Quist, David A., Herzog, Austin E., Schaefer, Andrew W., Kipouros, Ioannis, Bhadra, Mayukh, Solomon, Edward I., Karlin, Kenneth D.
Format: Article
Language:English
Subjects:
Bonding strength
Chemistry
Coordination compounds
Copper compounds
Disauerstoff-Reduktion
Hydrogen bonding
Hydrogen bonds
Kupfermonooxygenase
Kupfersuperoxid
Oxidation
Phenolic compounds
Phenols
Physical properties
Reactivity
Spectroscopy
Substrates
Superoxide
Wasserstoffatomtransfer
Wasserstoffbrücken
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Summary: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)CuII(O2.−)]+ cupric superoxide species was achieved, and they were characterized by resonance Raman (rR) spectroscopy. The structures and physical properties of [((X1)(X2) TMPA)CuII(N3−)]+ azido analogues were compared, and the O2.− reactivity of ligand–CuI 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. Kleiner Helfer H‐Brücke: Die Disauerstoff‐Reaktivität einer Reihe TMPA‐basierter Cu(I)‐Komplexe (TMPA=Tris(2‐pyridylmethyl)amin) wurde untersucht. Kinetische Stabilisierung der H‐Brücken‐gebundenen Kupfersuperoxid‐Spezies [((X1)(X2) ▪TMPA)CuII(O2.−)]+ wurde mit X1/X2=−NH2 und/oder Pivalamido (−HNC(O)C(CH3)3) erreicht. Die Komplexe zeigen eine hohe Reaktivität gegenüber Phenolsubstraten und Substraten mit moderaten C‐H‐Bindungsdissoziationsenergien.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201908471