Synthesis and Spectroscopic Properties of “Charge‐Inverted” Bis‐benzenedithiolato Complexes of Copper and Nickel

Quaternization of a phosphane‐functionalized benzene‐dithiol gave a phosphonio‐decorated product, which was reacted with copper and nickel salts to yield cationic metal‐bis(benzenedithiolene) complexes. Both the ligand and its complexes were fully characterized. The properties of the complexes were...

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Published inZeitschrift für anorganische und allgemeine Chemie (1950) Vol. 643; no. 21; pp. 1628 - 1634
Main Authors Schlindwein, Simon H., Ringenberg, Mark R., Nieger, Martin, Gudat, Dietrich
Format Journal Article
LanguageEnglish
Published Weinheim Wiley Subscription Services, Inc 17.11.2017
Subjects
Benzene
Cations
Coordination compounds
Copper
Cyclic voltammetry
Electron transfer
Electronic structure
Nickel
Oxidation
Redox chemistry
S ligands
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Summary:Quaternization of a phosphane‐functionalized benzene‐dithiol gave a phosphonio‐decorated product, which was reacted with copper and nickel salts to yield cationic metal‐bis(benzenedithiolene) complexes. Both the ligand and its complexes were fully characterized. The properties of the complexes were compared with those of previously known anionic complexes featuring identical metal coordination environments. UV/Vis and EPR studies indicate that the charge inversion induces only minor perturbations of the electronic structure of the complexes. Electrochemical studies indicated that the cationic species are more easily reducible and allowed to establish an unprecedented three‐membered electron transfer series involving +3/+2/+1 metal oxidation states of a copper bis‐dithiolene complex.
ISSN:0044-2313
1521-3749
DOI:10.1002/zaac.201700256