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Synthesis and Spectroscopic Properties of “Charge‐Inverted” Bis‐benzenedithiolato Complexes of Copper and Nickel
Author(s) -
Schlindwein Simon H.,
Ringenberg Mark R.,
Nieger Martin,
Gudat Dietrich
Publication year - 2017
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201700256
Subject(s) - nickel , copper , cationic polymerization , chemistry , electron paramagnetic resonance , metal , electrochemistry , benzene , dithiol , polymer chemistry , zinc , ligand (biochemistry) , yield (engineering) , inorganic chemistry , photochemistry , crystallography , organic chemistry , materials science , electrode , biochemistry , physics , receptor , nuclear magnetic resonance , metallurgy
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.