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Title: Reactivity of bio-inspired Cu(II) (N2/Py2) complexes with peroxide at room temperature

Abstract

Developing coordination complexes of earth abundant metals that can perform substrate oxidations under benign conditions is an ongoing challenge. Here, the reactivity of two mononuclear Cu-complexes toward the oxidant H 2O 2 is reported. Both complexes displayed ligand oxidation upon reaction with the oxidant. Analysis of spectroscopic data established that the respective product complexes contained mononuclear Cu(II) centers. Moreover, treatment of these Cu-complexes with oxidant in the presence of substrate resulted in the interception of ligand oxidation with preferential oxidation of the substrate. Computational studies identified plausible mechanistic pathways, suggesting a copper-oxyl intermediate as the likely reactive intermediate responsible for substrate and ligand oxidation. To our knowledge, this is the first Cu-mediated system that showed ligand oxidation, oxo-transfer capability, and external hydrocarbon oxidation under stoichiometric conditions.

Authors:
 [1];  [1];  [1]; ORCiD logo [2];  [3];  [2];  [3];  [1]
  1. Univ. of Alabama in Huntsville, Huntsville, AL (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1542780
Report Number(s):
BNL-211875-2019-JAAM
Journal ID: ISSN 0162-0134
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Inorganic Biochemistry
Additional Journal Information:
Journal Volume: 197; Journal Issue: C; Journal ID: ISSN 0162-0134
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; Cu-complexes reactivity with peroxide; Hydrocarbon oxidation

Citation Formats

Singh, Nirupama, Botcha, Niharika Krishna, Jones, Thomas M., Ertem, Mehmed Z., Niklas, Jens, Farquhar, Erik R., Poluektov, Oleg G., and Mukherjee, Anusree. Reactivity of bio-inspired Cu(II) (N2/Py2) complexes with peroxide at room temperature. United States: N. p., 2019. Web. doi:10.1016/j.jinorgbio.2019.03.014.
Singh, Nirupama, Botcha, Niharika Krishna, Jones, Thomas M., Ertem, Mehmed Z., Niklas, Jens, Farquhar, Erik R., Poluektov, Oleg G., & Mukherjee, Anusree. Reactivity of bio-inspired Cu(II) (N2/Py2) complexes with peroxide at room temperature. United States. doi:10.1016/j.jinorgbio.2019.03.014.
Singh, Nirupama, Botcha, Niharika Krishna, Jones, Thomas M., Ertem, Mehmed Z., Niklas, Jens, Farquhar, Erik R., Poluektov, Oleg G., and Mukherjee, Anusree. Thu . "Reactivity of bio-inspired Cu(II) (N2/Py2) complexes with peroxide at room temperature". United States. doi:10.1016/j.jinorgbio.2019.03.014.
@article{osti_1542780,
title = {Reactivity of bio-inspired Cu(II) (N2/Py2) complexes with peroxide at room temperature},
author = {Singh, Nirupama and Botcha, Niharika Krishna and Jones, Thomas M. and Ertem, Mehmed Z. and Niklas, Jens and Farquhar, Erik R. and Poluektov, Oleg G. and Mukherjee, Anusree},
abstractNote = {Developing coordination complexes of earth abundant metals that can perform substrate oxidations under benign conditions is an ongoing challenge. Here, the reactivity of two mononuclear Cu-complexes toward the oxidant H2O2 is reported. Both complexes displayed ligand oxidation upon reaction with the oxidant. Analysis of spectroscopic data established that the respective product complexes contained mononuclear Cu(II) centers. Moreover, treatment of these Cu-complexes with oxidant in the presence of substrate resulted in the interception of ligand oxidation with preferential oxidation of the substrate. Computational studies identified plausible mechanistic pathways, suggesting a copper-oxyl intermediate as the likely reactive intermediate responsible for substrate and ligand oxidation. To our knowledge, this is the first Cu-mediated system that showed ligand oxidation, oxo-transfer capability, and external hydrocarbon oxidation under stoichiometric conditions.},
doi = {10.1016/j.jinorgbio.2019.03.014},
journal = {Journal of Inorganic Biochemistry},
number = C,
volume = 197,
place = {United States},
year = {2019},
month = {3}
}

Journal Article:
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This content will become publicly available on March 21, 2020
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