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Analysis of a Diimine‐Organonickel Redox Series
Author(s) -
Sondermann Christina,
Pižl Martin,
Paretzki Alexa,
Feil Christoph,
Ringenberg Mark R.,
Záliš Stanislav,
Kaim Wolfgang
Publication year - 2020
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.202000455
Subject(s) - chemistry , redox , electron paramagnetic resonance , diimine , yield (engineering) , metal , cyclic voltammetry , electrochemistry , crystallography , medicinal chemistry , photochemistry , stereochemistry , inorganic chemistry , organic chemistry , catalysis , nuclear magnetic resonance , physics , materials science , metallurgy , electrode
Complex cations [Ni(C 5 R 5 )(L)] + , L = 1,4‐diphenyl‐2,3‐dimethyl‐1,4‐diaza‐1,3‐butadiene, were compared as structurally characterized BF 4 – (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(C 5 Me 5 )(L)] 0 and [Ni(C 5 Me 5 )(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 · – ).