Molecular and electronic structures of one-electron oxidized Ni(II)-(dithiosalicylidenediamine) complexes: Ni(III)-thiolate versus Ni(II)-thiyl radical states

Chemistry : a European Journal
Philip A StensonMartin Schröder

Abstract

The dithiosalicylidenediamine Ni II complexes [Ni(L)] (R=tBu, R'=CH2C(CH3)2CH2 1, R'=C6H4 2; R=H, R'=CH2C(CH3)2CH2 3, R'=C6H4 4) have been prepared by transmetallation of the tetrahedral complexes [Zn(L)] (R=tBu, R'=CH2C(CH3)2CH2 7, R'=C6H4 8; R=H, R'=CH2C(CH3)2CH2 9, R'=C6H4 10) formed by condensation of 2,4-di-R-thiosalicylaldehyde with diamines H2N-R'-NH2 in the presence of Zn II salts. The diamagnetic mononuclear complexes [Ni(L)] show a distorted square-planar N2S2 coordination environment and have been characterized by 1H- and 13C NMR and UV/Vis spectroscopies and by single-crystal X-ray crystallography. Cyclic voltammetry and coulombic measurements have established that complexes 1 and 2, incorporating tBu functionalities on the thiophenolate ligands, undergo reversible one-electron oxidation processes, whereas the analogous redox processes for complexes 3 and 4 are not reversible. The one-electron oxidized species, 1+ and 2+, can be generated quantitatively either electrochemically or chemically with 70 % HClO4. EPR and UV/Vis spectroscopic studies and supporting DFT calculations suggest that the SOMOs of 1+ and 2+ possess thiyl radical character, whereas those of 1(py)2 + and 2(py)2 + possess formal Ni III centers. Spe...Continue Reading

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Citations

Apr 15, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·F Thomas
Jul 20, 2018·Chemistry : a European Journal·Jyun-An YanHua-Fen Hsu
Jul 28, 2010·Angewandte Chemie·Johannes DömerF Ekkehardt Hahn
Jan 12, 2012·Angewandte Chemie·Adam NeubaGerald Henkel
Apr 11, 2014·Angewandte Chemie·Marcello GennariCarole Duboc
Nov 13, 2008·Inorganic Chemistry·Maurice van GastelWolfgang Lubitz
May 8, 2015·Chemical Reviews·Jason A Denny, Marcetta Y Darensbourg
Feb 12, 2017·Journal of the American Chemical Society·Nicole M MewsHartmut Schubert

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