In:
Angewandte Chemie International Edition, Wiley, Vol. 54, No. 42 ( 2015-10-12), p. 12506-12510
Kurzfassung:
A complete series of biomimetic [2Fe‐2S] clusters, [(L Dep Fe) 2 (μ‐S) 2 ] ( 3 , L Dep =CH[CMeN(2,6‐Et 2 C 6 H 3 )] 2 ), [(L Dep Fe) 2 (μ‐S) 2 K] ( 4 ), [(L Dep Fe) 2 (μ‐S) 2 ][Bu 4 N] ( 5 , Bu=n‐butyl), and [(L Dep Fe) 2 (μ‐S) 2 K 2 ] ( 6 ), could be synthesized and characterized. The all‐ferric [2Fe‐2S] cluster 3 is readily accessible through the reaction of [(L Dep Fe) 2 (μ‐H) 2 ] ( 2 ) with elemental sulfur. The chemical reduction of 3 with one molar equivalent of elemental potassium affords the contact ion pair K + [2Fe‐2S] − ( 4 ) as a one‐dimensional coordination polymer, which in turn reacts with [Bu 4 N]Cl to afford the separate ion pair [Bu 4 N] + [2Fe‐2S] − ( 5 ). Further reduction of 4 with potassium furnishes the super‐reduced all‐ferrous [2Fe‐2S] cluster 6 . Remarkably, complexes 4 and 5 are [2Fe‐2S] clusters with extensively delocalized Fe 2+ Fe 3+ pairs as evidenced by 57 Fe Mössbauer, X‐ray absorption and emission spectroscopy (XAS, XES) and in accordance with DFT calculations.
Materialart:
Online-Ressource
ISSN:
1433-7851
,
1521-3773
DOI:
10.1002/anie.201506788
Sprache:
Englisch
Verlag:
Wiley
Publikationsdatum:
2015
ZDB Id:
2011836-3
ZDB Id:
123227-7
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