Belle, Catherine

David, David

David, Rolf

Gellon, Gisèle

Gennarini, Federica

Isaac, James

Jamet, Hélène

Le Mest, Yves

Le Poul, Nicolas

López, Isidoro

Molton, Florian

Philouze, Christian

Réglier, Marius

Thibon-Pourret, Aurore

Wojcik, Laurianne

Hal - Université Grenoble Alpes

Effect of Monoelectronic Oxidation of an Unsymmetrical Phenoxido-Hydroxido Bridged Dicopper(II) Complex

HAL-Université de Bretagne Occidentale

HAL AMU

A (μ-hydroxido,
μ-phenoxido)­CuIICuII complex 1 has been synthesized using an unsymmetrical ligand bearing
an N,N-bis­(2-pyridyl)­methylamine
(BPA) moiety coordinating one copper and a dianionic bis-amide moiety
coordinating the other copper­(II) ion. Electrochemical mono-oxidation
of the complex in DMF occurs reversibly at 213 K at E1/2 = 0.12 V vs Fc+/Fc through a metal-centered
process. The resulting species (complex 1+) is only stable at low temperature and has been spectroscopically
characterized by UV–vis–NIR cryo-spectroelectrochemical
and EPR methods. DFT and TD-DFT calculations, consistent with experimental
data, support the formation of a CuIICuIII phenoxido-hydroxido
complex. Low-temperature chemical oxidation of 1 by NOSbF6 yields a tetranuclear complex 2­(SbF6)­(NO2) which displays two binuclear CuIICuII subunits. The X-ray crystal structure of 2(SbF6)­(NO2) evidences that the
nitrogen of the terminal amide group is protonated and the coordination
of the amide occurs via the O atom. The bis-amide moiety appears to
be a non-innocent proton acceptor along the redox process. Alternatively,
protonation of complex 1 leads to the complex 2(ClO4)2, as evidenced by X-ray crystallography,
cyclic voltammetry, and 1H NMR

Aurore Thibon-Pourret (2937102)

Federica Gennarini (2937099)

Rolf David (2821168)

James A. Isaac (2937096)

Isidoro Lopez (5758838)

Gisèle Gellon (1705132)

Florian Molton (1405567)

Laurianne Wojcik (4557640)

Christian Philouze (1405570)

David Flot (353774)

Yves Le Mest (1791775)

Marius Réglier (1293408)

Nicolas Le Poul (1431295)

Hélène Jamet (1705123)

Catherine Belle (1705135)

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Effect of Monoelectronic Oxidation of an Unsymmetrical
Phenoxido-Hydroxido Bridged Dicopper(II) Complex

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https://figshare.com/articles/Effect_of_Monoelectronic_Oxidation_of_an_Unsymmetrical_Phenoxido-Hydroxido_Bridged_Dicopper_II_Complex/7098830

Effect of Monoelectronic Oxidation of an Unsymmetrical Phenoxido-Hydroxido Bridged Dicopper(II) Complex

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Hal - Université Grenoble Alpes

HAL-Université de Bretagne Occidentale

HAL AMU

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