A Tetracopper(II)-Tetraradical cuboidal core and its reactivity as a functional model of phenoxazinone synthase

Publication type:
Journal article
Metadata:
Autoren
  • Chandan Mukherjee
  • Thomas Weyhermuller
  • Eberhard Bothe
  • Eva Rentschier
  • Phalguni Chaudhuri
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000250732000047&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1021/ic7012599
eISSN
1520-510X
Externe Identifier
  • Clarivate Analytics Document Solution ID: 228LS
  • PubMed Identifier: 17939654
ISSN
0020-1669
Ausgabe der Veröffentlichung
23
Zeitschrift
INORGANIC CHEMISTRY
Paginierung
9895 - 9905
Datum der Veröffentlichung
2007
Status
Published
Titel
A Tetracopper(II)-Tetraradical cuboidal core and its reactivity as a functional model of phenoxazinone synthase
Sub types
  • Article
Ausgabe der Zeitschrift
46

Data source: Web of Science (Lite)

Other metadata sources:
Autoren
  • Chandan Mukherjee
  • Thomas Weyhermüller
  • Eberhard Bothe
  • Eva Rentschler
  • Phalguni Chaudhuri
DOI
10.1021/ic7012599
eISSN
1520-510X
ISSN
0020-1669
Ausgabe der Veröffentlichung
23
Zeitschrift
Inorganic Chemistry
Sprache
en
Online publication date
2007
Paginierung
9895 - 9905
Datum der Veröffentlichung
2007
Status
Published
Herausgeber
American Chemical Society (ACS)
Herausgeber URL
http://dx.doi.org/10.1021/ic7012599
Datum der Datenerfassung
2023
Titel
A Tetracopper(II)-Tetraradical Cuboidal Core and Its Reactivity as a Functional Model of Phenoxazinone Synthase
Ausgabe der Zeitschrift
46

Data source: Crossref

Abstract
The coordination chemistry of the tridentate ligand N-(2-hydroxy-3,5-di-tert-butylphenyl)-2-aminobenzylalcohol H3L has been studied with the copper(II) ion. The ligand is noninnocent in the sense that it is readily oxidized in the presence of air to its o-iminobenzosemiquinonato [L*]2- radical form. The crystal structure of the synthesized tetracopper(II)-tetraradical complex [CuII4(L*)4] (1), has been determined by X-ray crystallography at 100 K. Variable-temperature (2-290 K) magnetic susceptibility measurements of complex 1 containing eight paramagnetic centers establish the spin ground state to be diamagnetic (St=0) arising from the antiferromagnetic interactions. Electrochemical measurements (cyclic voltammograms and square wave voltammograms) indicate four one-electron reductions of the ligand prior to the reduction of the metal center. Complex 1 is found to catalyze the aerial oxidation of 2-aminophenol to 2-amino-phenoxazine-3-one, thus modeling the catalytic function of the copper-containing enzyme phenoxazinone synthase. Kinetic measurements together with electron paramagnetic resonance and electronic spectral studies have been used to decipher the complex six-electron oxidative coupling of 2-aminophenol. An "on-off" mechanism of the radicals together with redox participation of the metal center is proposed for the catalytic oxidation processes.
Addresses
  • Institute for Inorganic and Analytical Chemistry, University of Mainz, D-55128 Mainz, Germany.
Autoren
  • Chandan Mukherjee
  • Thomas Weyhermüller
  • Eberhard Bothe
  • Eva Rentschler
  • Phalguni Chaudhuri
DOI
10.1021/ic7012599
eISSN
1520-510X
Externe Identifier
  • PubMed Identifier: 17939654
Open access
false
ISSN
0020-1669
Ausgabe der Veröffentlichung
23
Zeitschrift
Inorganic chemistry
Schlüsselwörter
  • Copper
  • Oxidoreductases
  • Crystallography, X-Ray
  • Spectrophotometry, Infrared
  • Magnetic Resonance Spectroscopy
  • Spectrometry, Mass, Electrospray Ionization
  • Electrochemistry
  • Magnetics
  • Models, Molecular
Sprache
eng
Medium
Print-Electronic
Online publication date
2007
Paginierung
9895 - 9905
Datum der Veröffentlichung
2007
Status
Published
Datum der Datenerfassung
2007
Titel
A tetracopper(II)-tetraradical cuboidal core and its reactivity as a functional model of phenoxazinone synthase.
Sub types
  • Research Support, Non-U.S. Gov't
  • Journal Article
Ausgabe der Zeitschrift
46

Data source: Europe PubMed Central

Abstract
The coordination chemistry of the tridentate ligand N-(2-hydroxy-3,5-di-tert-butylphenyl)-2-aminobenzylalcohol H3L has been studied with the copper(II) ion. The ligand is noninnocent in the sense that it is readily oxidized in the presence of air to its o-iminobenzosemiquinonato [L*]2- radical form. The crystal structure of the synthesized tetracopper(II)-tetraradical complex [CuII4(L*)4] (1), has been determined by X-ray crystallography at 100 K. Variable-temperature (2-290 K) magnetic susceptibility measurements of complex 1 containing eight paramagnetic centers establish the spin ground state to be diamagnetic (St=0) arising from the antiferromagnetic interactions. Electrochemical measurements (cyclic voltammograms and square wave voltammograms) indicate four one-electron reductions of the ligand prior to the reduction of the metal center. Complex 1 is found to catalyze the aerial oxidation of 2-aminophenol to 2-amino-phenoxazine-3-one, thus modeling the catalytic function of the copper-containing enzyme phenoxazinone synthase. Kinetic measurements together with electron paramagnetic resonance and electronic spectral studies have been used to decipher the complex six-electron oxidative coupling of 2-aminophenol. An "on-off" mechanism of the radicals together with redox participation of the metal center is proposed for the catalytic oxidation processes.
Autoren
  • Chandan Mukherjee
  • Thomas Weyhermüller
  • Eberhard Bothe
  • Eva Rentschler
  • Phalguni Chaudhuri
Autoren-URL
https://www.ncbi.nlm.nih.gov/pubmed/17939654
DOI
10.1021/ic7012599
ISSN
0020-1669
Ausgabe der Veröffentlichung
23
Zeitschrift
Inorg Chem
Schlüsselwörter
  • Copper
  • Crystallography, X-Ray
  • Electrochemistry
  • Magnetic Resonance Spectroscopy
  • Magnetics
  • Models, Molecular
  • Oxidoreductases
  • Spectrometry, Mass, Electrospray Ionization
  • Spectrophotometry, Infrared
Sprache
eng
Country
United States
Paginierung
9895 - 9905
Datum der Veröffentlichung
2007
Status
Published
Datum, an dem der Datensatz öffentlich gemacht wurde
2008
Titel
A tetracopper(II)-tetraradical cuboidal core and its reactivity as a functional model of phenoxazinone synthase.
Sub types
  • Journal Article
  • Research Support, Non-U.S. Gov't
Ausgabe der Zeitschrift
46

Data source: PubMed

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