The EPR spectra of the five-coordinated complexes [CoX(Me6tren)]Y (Me6tren = tris[2-(dimethylamino)ethyl]amine; X = C1, Br, I; Y = C1, Br, I, BPh,) and [CoX(np3)]Y (np3 = tris[2-(diphenylphosphino)ethyl]amine; X = CI, Br, I; Y = PFs, BPh4) have been recorded. The Me6tren complexes were found to yield g,, = 2 and g, = 4, in agreement with a ground Kramers doublet. No 59C0 hyperfine was resolved. The np3 complexes were found to give a gvalue in the range 6-7, but no other signal could be detected in the range 0-1.40 T. Single-crystal analysis showed that the g = 6-7 value is found parallel to the cobalt-axial ligand direction. The angular dependence of the spectra confirmed that the other two g values must be smaller than 0.45 and therefore outside the range available to our spectrometer. These data have been interpreted as indicative of a ground &3/2 Kramers doublet. The spin Hamiltonian parameters of the two sets of complexes have been justified on an angular overlap model
ESR spectra of low-symmetry high-spin cobalt(II) complexes. 10. Five-coordinated trigonal-bipyramidal complexes / C. Benelli;D. Gatteschi. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - STAMPA. - 21:(1982), pp. 1788-1790. [10.1021/ic00135a019]
ESR spectra of low-symmetry high-spin cobalt(II) complexes. 10. Five-coordinated trigonal-bipyramidal complexes
BENELLI, CRISTIANO;GATTESCHI, DANTE
1982
Abstract
The EPR spectra of the five-coordinated complexes [CoX(Me6tren)]Y (Me6tren = tris[2-(dimethylamino)ethyl]amine; X = C1, Br, I; Y = C1, Br, I, BPh,) and [CoX(np3)]Y (np3 = tris[2-(diphenylphosphino)ethyl]amine; X = CI, Br, I; Y = PFs, BPh4) have been recorded. The Me6tren complexes were found to yield g,, = 2 and g, = 4, in agreement with a ground Kramers doublet. No 59C0 hyperfine was resolved. The np3 complexes were found to give a gvalue in the range 6-7, but no other signal could be detected in the range 0-1.40 T. Single-crystal analysis showed that the g = 6-7 value is found parallel to the cobalt-axial ligand direction. The angular dependence of the spectra confirmed that the other two g values must be smaller than 0.45 and therefore outside the range available to our spectrometer. These data have been interpreted as indicative of a ground &3/2 Kramers doublet. The spin Hamiltonian parameters of the two sets of complexes have been justified on an angular overlap modelFile | Dimensione | Formato | |
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