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<p>Among all enzymatic metallocofactors, those found in nitrogenases, the P and L or M clusters, stand out for their intricate structures. They are assembled by proteins of the Nif gene cluster from Fe<sub>2</sub>S<sub>2</sub> rhombs—the smallest building blocks in FeS cluster chemistry—through a sequence of reactions constructing a Fe<sub>8</sub>S<sub>8</sub> precursor. To advance our understanding of how enzymes selectively build such elaborate inorganic molecules, here we parallel the biosynthetic pathway by reporting the rational stepwise assembly of [Fe<sub>8</sub>S<sub>8</sub>]<sup><i>m+</i></sup> (<i>m</i> = 2, 4, 6) clusters from [Fe<sub>2</sub>S<sub>2</sub>]<sup>2+</sup> rhombs within an extensive cyclic synthetic network. A [Fe<sub>8</sub>S<sub>8</sub>]<sup>4+</sup> cluster of unique topology is identified, for which we coin the term ‘interlocked’ double cubane. As a molecular analogue of the NifB K cluster, a proposed precursor to both the P and L or M clusters, its preparation and the characterization of all related intermediates, offers fundamental insights into the molecular mechanisms governing the assembly of both biogenic and synthetic FeS clusters.</p><p></p>

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Stepwise and reversible assembly of [2Fe–2S] rhombs to [8Fe–8S] clusters and their topological interconversions

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年8月20日

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  • Liam Grunwald,
  • Micha L. Weber,
  • Henrik Seng,
  • Martin Clémancey,
  • Patrick Dubourdeaux,
  • Hongxin Wang,
  • Michael Wörle,
  • Yoshitaka Yoda,
  • Stephen P. Cramer,
  • Geneviève Blondin,
  • Victor Mougel

摘要

Among all enzymatic metallocofactors, those found in nitrogenases, the P and L or M clusters, stand out for their intricate structures. They are assembled by proteins of the Nif gene cluster from Fe2S2 rhombs—the smallest building blocks in FeS cluster chemistry—through a sequence of reactions constructing a Fe8S8 precursor. To advance our understanding of how enzymes selectively build such elaborate inorganic molecules, here we parallel the biosynthetic pathway by reporting the rational stepwise assembly of [Fe8S8]m+ (m = 2, 4, 6) clusters from [Fe2S2]2+ rhombs within an extensive cyclic synthetic network. A [Fe8S8]4+ cluster of unique topology is identified, for which we coin the term ‘interlocked’ double cubane. As a molecular analogue of the NifB K cluster, a proposed precursor to both the P and L or M clusters, its preparation and the characterization of all related intermediates, offers fundamental insights into the molecular mechanisms governing the assembly of both biogenic and synthetic FeS clusters.