Abstract
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 LSCoIII and HSCoII 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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According to the materials of the International Conference “Organometallic and Coordination Chemistry: Fundamental and Applied Aspects” (September 1–7, 2013, Nizhny Novgorod).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 0812–0820, April, 2014.
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Starikova, A.A., Minyaev, R.M. & Minkin, V.I. Computational design of mixed-ligand adducts of Co aminovinyl ketonates with redox-active o-quinones and their derivatives. Russ Chem Bull 63, 812–820 (2014). https://doi.org/10.1007/s11172-014-0514-x
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DOI: https://doi.org/10.1007/s11172-014-0514-x