Single-crystal and powder EPR studies of the S = 1/4 ground state of the iron-sulfur core in [tris(tetraethylammonium)]-[tetrakis(benzylthiolato)tetrakis(μ3-sulf ido)tetrairon]· (N,N-dimethylformamide) with crystal structure determination

Journal of the American Chemical Society

Volumn 118, Issue 46, 1996, Pages 11644-11653

  Gloux, Jocelyne ^a,b   Gloux, Pierre ^a,c   Laugier, Jean ^a  

^a CEA GRENOBLE   (France)

^b UNIV GRENOBLE ALPES   (France)

^c CNRS   (France)

Author keywords

[No Author keywords available]

Indexed keywords

IRON COMPLEX;

ARTICLE; CRYSTALLOGRAPHY; DRUG STRUCTURE; ELECTRON SPIN RESONANCE;

EID: 0029923938     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja961396a     Document Type: Article

References (30)

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12. 4), the splitting of the ferrous 3d orbitals is found to depend on the orientation of the S-C bond (Gebhard, M. S.; Koch, S. A.; Millar, M.; Devlin, F. J.; Stephens, P. J.; Solomon, E. I. J. Am. Chem. Soc. 1991, 113, 1640).
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17. This set of values cannot be fitted by the diagrams of effective g values in terms of the rhombicity λ given in ref 15 for the Kramers doublets of a pure spin S = 3/2 (isotropic real g value of 2). We explained the g value set by an effective spin S = 3/2 with λ ≅ 1/3 and real g values around 1.9 (see ref 4).
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22. + clusters.
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28. + cluster in the active form of the metalloenzyme Ni-Fe hydrogenase of Desulfovibrio gigas, good simulations of the experimental multi-frequency EPR spectra are achieved only when it is the principal direction of intermediate g value that is taken to be nearly perpendicular to both the mixed-valence pair and the ferrous pair (Bertrand, P.; Camensuli, P.; More, C.; Guigliarelli, B. J. Am. Chem. Soc. 1996, 118, 1426).
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30. + clusters in the case of proteins, the low symmetry environment provided by the protein could be responsible for the fact that essentially S = 1/2 ground states are observed experimentally.