Ground term splitting of high-spin cobalt(2+) ion as a probe of coordination structure. 1. Dependence of the splitting on coordination geometry
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The sign and magnitude of the splitting between the two lowest Kramers doublets (Δ) of high-spin Co2+ in a variety of structurally defined, small molecule coordination complexes is determined. The range of values of Δ is found to be <13 cm-1 in tetracoordinate sites, ~20-50 cm-1 in pentacoordinate sites of trigonal-bipyramidal or square-pyramidal geometry, and ≥50 cm-1 in hexacoordinate sites. It is shown on the basis of group theoretical arguments and estimates of the zero-field splitting derived by second-order perturbation theory that the observed range of values of Δ correlates well with that predicted by theory. On this basis, it is suggested that the splitting between the two lowest Kramers doublets of high-spin Co2+ may provide a diagnostic signature of coordination geometry. © 1985, American Chemical Society. All rights reserved.
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Journal of the American Chemical Society
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Makinen, M. W., Kuo, L. C., Yim, M. B., Wells, G. B., Fukuyama, J. M., & Kim, J. E
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Makinen, Marvin W||Kuo, Lawrence C||Yim, Moon B||Wells, Gregg B||Fukuyama, James M||Kim, Judy E
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