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Synthesis and crystal structure of the cubane-like cluster [(Tp*)MoFe<sub>3</sub>S<sub>3</sub>(μ<sub>3</sub>-Cl)(PMe<sub>3</sub>)<sub>3</sub>](BPh<sub>4</sub>).

Acta crystallographica. Section E, Crystallographic communications·2026
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Synthesis and crystal structure of a mixed-metal 3D coordination polymer poly[[bis-(μ<sub>5</sub>-anthra-quinone-1,8-di-sulfonato-κ<sup>5</sup> <i>O</i>:<i>O</i>':<i>O</i>'':<i>O</i>''':<i>O</i>'''')di-μ<sub>2</sub>-aqua-κ<sup>4</sup> <i>O</i>:<i>O</i>-tetra-aqua-copper(II)disodium] dihydrate].

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Synthetic models of the nitrogenase FeMo cofactor.

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Stepwise Construction of Mo-Fe-S Clusters Using a LEGO Strategy.

Juan He1, Jia Wei1, Gan Xu1

  • 1Jiangsu Collaborative Innovation Center of Biomedical Functional Materials and Jiangsu Key Laboratory of New Power Batteries, School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, Jiangsu, China.

Inorganic Chemistry
|February 24, 2022
PubMed
Summary

Researchers developed a LEGO-like strategy to rationally synthesize versatile molybdenum-iron-sulfur (Mo-Fe-S) cubane clusters. This method allows for controlled ligand substitution, creating new possibilities for biomimetic chemistry, particularly for nitrogenase active sites.

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Area of Science:

  • Inorganic Chemistry
  • Biomimetic Chemistry
  • Coordination Chemistry

Background:

  • Synthesizing iron-sulfur clusters with controlled ligands is challenging in biomimetic chemistry.
  • Nitrogenase and its iron-molybdenum (FeMo) cofactor are crucial for biological nitrogen fixation.

Purpose of the Study:

  • To develop a rational and versatile synthetic strategy for molybdenum-iron-sulfur (Mo-Fe-S) cubane clusters.
  • To enable controlled introduction of various ligands for biomimetic studies of nitrogenase.

Main Methods:

  • A stepwise "LEGO strategy" using distinct molecular "bricks" (Fe, S, Cl) was employed.
  • Assembly of incomplete (MoFe2S3Cl) and complete (MoFe3S3Cl) cubane cores from a MoS3 frame.
  • Ligand metathesis reactions to replace bridging chloride ligands with 2p donors (N, O, S).

Main Results:

  • Successfully constructed Mo-Fe-S cubane clusters with controlled stepwise assembly.
  • Demonstrated facile ligand exchange at bridging sites, introducing N, O, and S donors.
  • Generated diverse cluster cores including MoFe2S3N, MoFe2S3O, MoFe3S3N, and MoFe3S4.

Conclusions:

  • The "LEGO strategy" provides a versatile platform for synthesizing Mo-Fe-S clusters.
  • This methodology facilitates the creation of diverse biomimetic models for nitrogenase.
  • Offers new avenues for understanding and mimicking nitrogen fixation processes.