Reversible Double Oxidation and Protonation of the Non-Innocent Bridge in a Nickel(II) Salophen Complex.

Substitution on the arom. bridge of a Ni(II) salophen complex with electron-donating dimethylamino substituents creates a ligand with three stable, easily and reversibly accessible oxidn. states. The 1-electron-oxidized product was characterized as a Ni(II) radical complex with the radical bore by the central substituted arom. ring, in contrast to other Ni(II) salen or salophen complexes that oxidize on the phenolate moieties. The doubly oxidized product, a singlet species, is best described as having an iminobenzoquinone bridge with a vinylogous distribution of bond lengths between the dimethylamino substituents. Protonation of the dimethylamino substituents inhibits these redox processes on the time scale of cyclovoltammetry, but electrolysis and chem. oxidn. are consistent with deprotonation occurring concomitantly with electron transfer to yield the mono- and dioxidized species described above. [on SciFinder(R)]

Références

Titre
Reversible Double Oxidation and Protonation of the Non-Innocent Bridge in a Nickel(II) Salophen Complex.
Type de publication
Article de revue
Année de publication
2012
Revue
Inorg. Chem.
Volume
51
Pagination
12796–12804
ISSN
0020-1669
Soumis le 12 avril 2018