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 RongZhou JieChen Xu-DongHolm Richard H.

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

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

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Molybdenum-dependent nitrogenases catalyze the transformation of dinitrogen into ammonia under ambient conditions. The active site (FeMo cofactor) is the structurally and electronically complex weak-field metal cluster MoFe7S9C built of Fe4S3 and MoFe3S3C portions connected by three sulfur bridges and containing an interstitial carbon atom centered in an Fe-6 trigonal prism. Chemical synthesis of this cluster is a major challenge in biomimetic inorganic chemistry. One synthetic approach of core ligand metathesis has been developed based on the design and synthesis of unprecedented incomplete ((Tp*)WFe(2)S(3)Q(3)(-)) and complete ((Tp*)WFe(3)S(3)Q(4)(2-)) cubane-type clusters containing bridging halide (Q = halide). These clusters are achieved by template-assisted assembly in the presence of sodium benzophenone ketyl reductant; products are controlled by reaction stoichiometry. Incomplete cubane clusters are subject to a variety of metathesis reactions resulting in substitution of a mu(2)-bridging ligand with other bridges such as N-3(-), MeO-, and EtS-. Reactions of complete cubanes with Me3SiN3 and S-8 undergo a redox metathesis process and lead to core ligand displacement and formation of (Tp*)WFe3S3(mu(3)-Q)Cl-3(-) (Q = Me3SiN2-, S-2(-)). This work affords entry to a wide variety of heteroleptic clusters derivable from incomplete and complete cubanes; examples are provided. Among these is the cluster (Tp*)WFe3S3(mu(3)-NSiMe3)Cl-3(-), one of the very few instances of a synthetic Fe-S cluster containing a light atom (C, N, O) in the core, which constitutes a close mimic of the MoFe3S3C fragment in FeMo cofactor. Superposition of them and comparison of metric information disclose a clear structural relationship Tp* = tris(3,5-dimethyl-1-pyrazolyl) hydroborate(1-).

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《Proceedings of the National Academy of Sciences of the United States of America.》 |2018年第20期|5089-5092|共4页
作者
Xu Gan; Wang Zheng; Ling RongZhou JieChen Xu-DongHolm Richard H.;
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作者单位

Nanjing Normal Univ, Sch Chem & Mat Sci, Jiangsu Collaborat Innovat Ctr Biomed Funct Mat, Jiangsu Key Lab Biofunct Mat, Nanjing 210023, Jiangsu, Peoples R China;

Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA;

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收录信息美国《科学引文索引》(SCI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
原文格式 PDF
正文语种英语
中图分类自然科学总论;
关键词
ligand metathesis; tungsten-iron-sulfur clusters; cubane-type clusters; heteroleptic clusters; FeMo cofactor;

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

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