Analysis of a Diimine-Organonickel Redox Series

0536325 - ÚFCH JH 2021 RIV DE eng J - Journal Article
Sondermann, Ch. - Pižl, Martin - Paretzki, A. - Feil, Ch. - Ringenberg, M. R. - Záliš, Stanislav - Kaim, W.
Analysis of a Diimine-Organonickel Redox Series.
European Journal of Inorganic Chemistry. Roč. 2020, č. 31 (2020), s. 3010-3015. ISSN 1434-1948. E-ISSN 1099-0682
Institutional support: RVO:61388955
Keywords : alpha-diimine * nickel-complexes * electronic-structure * ethylene * spectroelectrochemistry * approximation * reactivity * mechanism * oxidation * catalysts * Cyclopentadienide ligands * Electron transfer * Nickel * Redox chemistry * Spectroelectrochemistry
OECD category: Physical chemistry
Impact factor: 2.524, year: 2020
Method of publishing: Limited access

Complex cations [Ni(C5R5)(L)](+), L = 1,4-diphenyl-2,3-dimethyl-1,4-diaza-1,3-butadiene, were compared as structurally characterized BF4-(R = H) and SbF(6)(-)salts (R = Me). These Ni-II(L-0) compounds are reversibly reduced (R = H,Me) or oxidized (R = Me) and their one-electron oxidized and reduced forms studied by EPR and UV/Vis spectroelectrochemistry, supported by DFT calculations. Surprisingly similar EPR features were observed for [Ni(C5Me5)(L)](0)and [Ni(C5Me5)(L)](2+). Whereas the oxidation is largely metal centered to yield a Ni(III)species (R = Me), the reduction reveals energetically close-lying alternatives (redox isomers) Ni-I(L-0) and Ni-II(L center dot-).
Permanent Link: http://hdl.handle.net/11104/0314109