In:
Angewandte Chemie, Wiley, Vol. 133, No. 29 ( 2021-07-12), p. 15926-15931
Abstract:
Constructing synthetic models of the nitrogenase P N ‐cluster has been a long‐standing synthetic challenge. Here, we report an optimal nitrogenase P N ‐cluster model [{(TbtS)(OEt 2 )Fe 4 S 3 } 2 (μ‐STbt) 2 (μ 6 ‐S)] ( 2 ) [Tbt=2,4,6‐tris{bis(trimethylsilyl)methyl}phenyl] that is the closest synthetic mimic constructed to date. Of note is that two thiolate ligands and one hexacoordinated sulfide are connecting the two Fe 4 S 3 incomplete cubanes similar to the native P N ‐cluster, which has never been achieved. Cluster 2 has been characterized by X‐ray crystallography and relevant physico‐chemical methods. The variable temperature magnetic moments of 2 indicate a singlet ground state ( S =0). The Mössbauer spectrum of 2 exhibits two doublets with an intensity ratio of 3:1, which suggests the presence of two types of iron sites. The synthetic pathway of the cluster 2 could indicate the native P N ‐cluster maturation process as it has been achieved from the Fe 4 S 4 cubane Fe 4 S 4 (STbt) 4 ( 1 ).
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v133.29
DOI:
10.1002/ange.202102369
Language:
English
Publisher:
Wiley
Publication Date:
2021
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