Redox noninnocence of the bridge in copper(II) salophen and bis(oxamato) complexes

Inorganic Chemistry
David de BellefeuilleFabrice Thomas

Abstract

Two square-planar copper(II) complexes of 1,2-bis(2-hydroxy-3,5-di-tert-butylbenzimino)-4,5-bis(dimethylamino)benzene (1) and N-[4,5-bis(dimethylamino)-2-(oxalylamino)benzene]oxamate (2(2-)) were prepared. The crystal structures of the proligands H2L(1) and Et2H2L(2), as well as the corresponding complexes, are reported. The proligands each display a one-electron-oxidation wave, which is assigned to oxidation of the bis(dimethylamino)benzene moiety into a π radical. Complexes 1 and 2(2-) exhibit reversible one-electron-oxidation waves in their cyclic voltammograms (E1/2(1) = 0.14 and E1/2(2) = 0.31 V for 1 and E1/2(1) = -0.47 V vs Fc(+)/Fc for 2(2-)). The first process corresponds to oxidation of the bis(dimethylamino)benzene central ring into a π radical, while the second process for 1 is ascribed to oxidation of the π radical into an α-diiminoquinone. The one-electron-oxidized species 1(+) and 2(-) exhibit intense visible-near-IR absorptions, which are diagnostic of π radicals. They display a triplet signal in their electron paramagnetic resonance spectra, which stem from magnetic coupling between the ligand-radical spin and the copper(II) spin. The zero-field-splitting parameters are larger for 2(-) than 1(+) because of grea...Continue Reading

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Citations

Jun 14, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Sara RealistaPaulo N Martinho
Oct 19, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Laureline LecarmeFabrice Thomas
Jun 18, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Guangli ZhanXiaoming Liu
Oct 6, 2017·Chemistry : a European Journal·Irene Mustieles MarínAudrey Auffrant
Aug 8, 2018·Chemistry : a European Journal·Jarl Ivar van der Vlugt

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