Analysis of a Diimine‐Organonickel Redox Series

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 SbF6– salts (R = Me). These NiII(L0) compounds are reversibly reduced (R = H,Me) or oxidized (R = Me) and their one‐electron oxidized and reduced forms...

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Published in:European journal of inorganic chemistry Vol. 2020; no. 31; pp. 3010 - 3015
Main Authors: Sondermann, Christina, Pižl, Martin, Paretzki, Alexa, Feil, Christoph, Ringenberg, Mark R., Záliš, Stanislav, Kaim, Wolfgang
Format: Journal Article
Language:English
Published: Weinheim Wiley Subscription Services, Inc 23.08.2020
Subjects:
Alternative energy sources
Butadiene
Cyclopentadienide ligands
Electron transfer
Inorganic chemistry
Isomers
Nickel
Oxidation
Redox chemistry
Spectroelectrochemistry
ISSN:1434-1948, 1099-0682
Online Access:Get full text
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Summary: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 SbF6– salts (R = Me). These NiII(L0) 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 NiIII species (R = Me), the reduction reveals energetically close‐lying alternatives (redox isomers) NiI(L0) and NiII(L·–). A rare case of innocent α‐diimine ligand behavior and mostly metal‐based electron transfer has been evidenced for [Ni(C5Me5)(L)]n, n = 0,+,2+, and L = 1,4‐diphenyl‐2,3‐dimethyl‐1,4‐diaza‐1,3‐butadiene via spectroelectrochemistry and DFT.
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ISSN:1434-1948
1099-0682
DOI:10.1002/ejic.202000455