Ligand metathesis as rational strategy for the synthesis of cubane-type heteroleptic iron–sulfur clusters relevant to the FeMo cofactor

Xu, Gan; Wang, Zheng; Ling, Rong; Zhou, Jie; Chen, Xu‐Dong; Holm, R. H.

doi:10.1073/pnas.1801025115

Cited by 36 publications

(50 citation statements)

References 18 publications

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“…In the single-crystal structures as evident in Figure 1, cluster anions 3a, b exhibit analogous centrosymmetric structures.T he cluster is constituted by connection of ap air of cubane-type subunit via two Fe-N edges in head-to-tail mode to form aFe 2 N 2 rhomb,inwhich both nitride ligands adopt m 4bridging mode.Within the rhomb of 3a,the intra-cubane Fe À Nb ond length on the bridging edge at 1.966 (5) is longer than the other two intra-cubane Fe-N contacts of 1.901(5) and 1.888(5) ,a sw ell as the inter-cubane Fe3-N1 i distance at 1.881 (5) .T he molecule also holds quasi-mirror symmetry upon the plane of Fe3-N1-Fe3 i -N1 i .T he average Fe À Nb ond length within the cubic subunit is 1.918(5) ,b eing slightly shorter than that of 1.936(3) in the reported imide bridged cubane cluster. [49] Theb ond length pattern is indicative of tight binding between subunits and Fe-N distances in this cluster are comparable with those for reported iron-nitride complexes with FeÀNs ingle bond [16,[42][43][44][45] (See Table S2 for alist of FeÀNb onds in selected iron nitride complexes).…”

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confidence: 86%

Controlled Incorporation of Nitrides into W‐Fe‐S Clusters

Zhou

Wang

et al. 2019

Angew Chem Int Ed

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Incorporation of monatomic 2p ligands into the core of iron-sulfur clusters has been researched since the discovery of interstitial carbide in the FeMo cofactor of Mo-dependent nitrogenase,but has proven to be asynthetic challenge.Herein, two distinct synthetic pathwaysa re rationalized to install nitride ligands into targeted positions of W-Fe-S clusters, generating unprecedented nitride-ligated iron-sulfur clusters, namely [(Tp*) 2 W 2 Fe 6 (m 4 -N) 2 S 6 L 4 ] 2À (Tp* = tris(3,5-dimethyl-1-pyrazolyl)hydroborate(1À), L = Cl À or Br À ). 57 Fe Mçssbauer study discloses metal oxidation states of W IV 2 Fe II 4 Fe III 2 with localized electron distribution, which is analogous to the midvalent iron centres of FeMo cofactor at resting state.G ood agreement of Mçssbauer data with the empirical linear relationship for Fe-S clusters indicates similar ligand behaviour of nitride and sulfide in such clusters,p roviding useful reference for reduced nitrogen in an itrogenase-like environment.Scheme 1. Distinct synthetic pathwayso fcluster 3.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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supporting

confidence: 86%

Controlled Incorporation of Nitrides into W‐Fe‐S Clusters

Zhou

Wang

et al. 2019

Angew Chem Int Ed

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“…The molecule also holds quasi‐mirror symmetry upon the plane of Fe3‐N1‐Fe3 i ‐N1 i . The average Fe−N bond length within the cubic subunit is 1.918(5) Å, being slightly shorter than that of 1.936(3) Å in the reported imide bridged cubane cluster . The bond length pattern is indicative of tight binding between subunits and Fe–N distances in this cluster are comparable with those for reported iron‐nitride complexes with Fe−N single bond (See Table S2 for a list of Fe−N bonds in selected iron nitride complexes).…”

Section: Methodssupporting

confidence: 69%

Controlled Incorporation of Nitrides into W‐Fe‐S Clusters

Zhou

Wang

et al. 2019

Angewandte Chemie

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Incorporation of monatomic 2p ligands into the core of iron–sulfur clusters has been researched since the discovery of interstitial carbide in the FeMo cofactor of Mo‐dependent nitrogenase, but has proven to be a synthetic challenge. Herein, two distinct synthetic pathways are rationalized to install nitride ligands into targeted positions of W‐Fe‐S clusters, generating unprecedented nitride‐ligated iron–sulfur clusters, namely [(Tp*)2W2Fe6(μ4‐N)2S6L4]2− (Tp*=tris(3,5‐dimethyl‐1‐pyrazolyl)hydroborate(1−), L=Cl− or Br−). 57Fe Mössbauer study discloses metal oxidation states of WIV2FeII4FeIII2 with localized electron distribution, which is analogous to the mid‐valent iron centres of FeMo cofactor at resting state. Good agreement of Mössbauer data with the empirical linear relationship for Fe–S clusters indicates similar ligand behaviour of nitride and sulfide in such clusters, providing useful reference for reduced nitrogen in a nitrogenase‐like environment.

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“…Embedding a carbon donor into analogues of the FeMo-co as an interstitial carbon for mimicking the biological nitrogenase is especially challenging. Xu et al [117] reported that a core halide ligand (Cl − or Br − ) replacing thiolate was incorporated into a binding site of the heterometallic clusters using one-electron reductant sodium benzophenone ketyl. The new approach provided opportunities to synthesize the analogues more similar to FeMo-co, because core halides are easily replaced with carbon ligands through metathesis reactions.…”

Section: Incorporating Carbon Atoms Into Femo-co Analoguesmentioning

confidence: 99%

Progress in Synthesizing Analogues of Nitrogenase Metalloclusters for Catalytic Reduction of Nitrogen to Ammonia

Yang

2019

Catalysts

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Ammonia (NH3) has played an essential role in meeting the increasing demand for food and the worldwide need for nitrogen (N2) fertilizer since 1913. Unfortunately, the traditional Haber–Bosch process for producing NH3 from N2 is a high energy-consumption process with approximately 1.9 metric tons of fossil CO2 being released per metric ton of NH3 produced. As a very challenging target, any ideal NH3 production process reducing fossil energy consumption and environmental pollution would be welcomed. Catalytic NH3 synthesis is an attractive and promising alternative approach. Therefore, developing efficient catalysts for synthesizing NH3 from N2 under ambient conditions would create a significant opportunity to directly provide nitrogenous fertilizers in agricultural fields as needed in a distributed manner. In this paper, the literature on alternative, available, and sustainable NH3 production processes in terms of the scientific aspects of the spatial structures of nitrogenase metalloclusters, the mechanism of reducing N2 to NH3 catalyzed by nitrogenase, the synthetic analogues of nitrogenase metalloclusters, and the opportunities for continued research are reviewed.

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Ligand metathesis as rational strategy for the synthesis of cubane-type heteroleptic iron–sulfur clusters relevant to the FeMo cofactor

Cited by 36 publications

References 18 publications

Controlled Incorporation of Nitrides into W‐Fe‐S Clusters

Controlled Incorporation of Nitrides into W‐Fe‐S Clusters

Controlled Incorporation of Nitrides into W‐Fe‐S Clusters

Progress in Synthesizing Analogues of Nitrogenase Metalloclusters for Catalytic Reduction of Nitrogen to Ammonia

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