Adducts of cobalt(II) bis(salicylaldiminates) and redox-active phenoxazin-1-one: synthesis, structure, and magnetic properties

作者：Antipin M Yu; Ivakhnenko E P; Koshchienko Yu V; Knyazev P A; Korobov M S; Chernyshev A V; Lyssenko K A; Starikov A G^*; Minkin V I

来源：Russian Chemical Bulletin, 2013, 62(8): 1744-1751.

DOI：10.1007/s11172-013-0251-6

• complexes
• phenoxazin-1-one
• magnetic properties
• valence tautomerism

Adducts of cobalt(II) bis(salicylaldiminates) and 2,4,6,8-tetra-tert-butylphenoxazin-1-one were synthesized and their molecular and crystal structures were determined. According to the ESR and magnetochemical data, the metal atom is in the low-spin trivalent state (Co-III) due to the intramolecular electron transfer to the redox-active ligand. In the solid state, the mixedligand complexes are stable in air for several months, but in solution at elevated temperatures they dissociate to the starting components. Such a behavior detected by the temperature dependence of the effective magnetic moment is explained by the quantum chemical DFT calculations of the energy barriers of possible valence tautomeric dynamics, whose values were found to be higher than the enthalpy of dissociation.

• 出版日期2013-8