Journal
RUSSIAN CHEMICAL BULLETIN
Volume 63, Issue 4, Pages 812-820Publisher
SPRINGER
DOI: 10.1007/s11172-014-0514-x
Keywords
complexes; o-benzoquinone; aminovinyl ketonates; magnetic properties; valence tautomerism; density functional theory; B3LYP functional
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Funding
- Russian Foundation for Basic Research [13-03-12418 ofi-m]
- Council for Grants at President of the Russian Federation [SP-1718.2013.5]
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The adducts of cobalt aminovinyl ketonates with o-benzoquinones, o-benzoquinone imines, and o-benzoquinone diimines were studied by the density functional theory method (B3LYP*/6-311++G(d,p)). For all of the compounds, the ground states are low-spin structures containing a trivalent cobalt atom and a redox-active ligand in the semiquinonate form. The bulky substituents at the bis-chelate and ligand nitrogen atoms favor a decrease in the energy difference between the low-spin and high-spin isomers of the adducts containing Co-LS(III) and Co-HS(II) atoms, respectively. These compounds can exhibit valence tautomerism in the crystalline state, but the relatively low stabilization energies of the high-spin isomers in solutions may induce a competing process: dissociation into the original bis-chelate and redox-active ligand.
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