Conformational tuning of valence delocalization in carboxylate-rich diiron complexes [20]

Journal of the American Chemical Society

Volumn 121, Issue 41, 1999, Pages 9760-9761

  Hagadorn, John R ^a   Que Jr , Lawrence ^a   Tolman, William B ^a   Prisecaru, Ion ^b   Münck, Eckard ^b  

^a University of Minnesota   (United States)

^b CARNEGIE MELLON UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBOXYLIC ACID DERIVATIVE; IRON COMPLEX; METALLOPROTEIN;

COMPLEX FORMATION; CONFORMATIONAL TRANSITION; CRYSTAL STRUCTURE; CRYSTALLIZATION; LETTER; MOSSBAUER SPECTROSCOPY; STEREOSPECIFICITY; ULTRAVIOLET SPECTROSCOPY;

EID: 0032748441     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja992038l     Document Type: Letter

References (29)

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8. Only one [2Fe-2S] ferredoxin has been found with an S = 9/2 ground state. (a) Achim, C.; Bominaar, E. L.; Meyer, J.; Peterson, J.; Münck, E. J. Am. Chem. Soc. 1999, 121, 3704-3714. [2Fe-2S] fragments with S = 9/2 exist in [3Fe-4S] and [4Fe-4S] clusters, see: (b) Beinert, H.; Holm, R. H.; Münck, E. Science 1997, 277, 653-659.
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19. 2, which has been structurally characterized (Supporting Information).
20. 3NO instead of dioxygen.
21. For 1, the average Fe-O bond lengths are 2.004 Å for Fe1 and 2.008 Å and Fe2 (Δ = 0.004 Å). The analogous values for 2 are 2.039 and 1.998 Å (Δ = 0.041 Å).
22. Crystal structures of both conformational isomers were done twice using independently crystallized batches to ensure reproducibility.
23. Preliminary data of solid 1 contain a major feature at g ≈ 10 that may result from the ±3/2 doublet of an S = 9/2 system with E/D ≈ 0.2.
24. The sample of 1, shown in Figure 2b, contained a contaminant of 2 (22%) and a high-spin ferrous impurity (6%). We have removed their contributions from the data.
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26. For six-line spectra, such as those of Figure 2, not all parameters are uniquely determined. Thus, there may exist an infinite manifold of {α,β,η} values that produce identical spectra. See ref 18.
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