Activation of unsaturated small molecules by bio-relevant multinuclear metal-sulfur clusters
Activation of unsaturated small molecules by bio-relevant multinuclear metal-sulfur clusters
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生物相关多核金属硫簇活化不饱和小分子
DOI：
10.1016/j.ccr.2022.214838
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发表时间：
2023
影响因子：
20.6
通讯作者：
Seino Hidetake
中科院分区：
文献类型：
--
作者：
Tanifuji Kazuki;Ohta Shun;Ohki Yasuhiro;Seino Hidetake
硫(S)对过渡金属离子(M)的高亲和力，以及灵活的M - S键和桥接模式，使得形成广泛的多金属化合物，称为金属-硫（M - S）簇。尽管M - S簇原则上可以容忍各种核，但分子实体中的金属数量，特别是那些适用于催化反应的金属数量，通常为4或更低，而在生物n2还原催化剂中发现的最高数量为8。在自然界中，除了n2还原外，M−S簇也存在于CO2、CO和H2等小分子的转化中。随着近年来生物化学研究对这些天然M - S簇的详细结构的阐明，我们可以朝着开发优于酶和/或生物上不可接近的反应的人工催化剂迈出一步，而另一个方向是深入了解酶反应及其与M - S结构之间的关系。本文综述了合成M - S簇的反应研究进展，重点介绍了它们在小分子活化和转化中的应用。本文的主要内容分为三个部分：1)n2及相关小分子的转化；2)CO2的还原；3)有机小分子的转化。近年来取得的显著进展包括催化n2 -硅化反应生成N(SiMe3)3和催化c1 - c4烃的co2还原。在过去的十年中，硝基芳烃的串联还原和n -甲基化也已经完成。通过回顾，发现M - S簇催化反应的发展仍然具有挑战性。能够合成M - S簇的化学家、擅长发展均相催化反应的化学家、拥有光谱技术的化学家和理论化学家之间的合作，可能会为这一领域提供新的见解。
The high affinity of sulfur (S) for transition metal ions (M), as well as the flexible M−S bonding and bridging modes, enable the formation of a wide range of multi-metallic compounds called metal-sulfur (M−S) clusters. Even though M−S clusters tolerate various nuclearities in principle, the number of metals in molecular entities, particularly those applicable in catalytic reactions, are typically 4 or lower, while the highest number of 8 has been found in the biological N2-reducing catalyst. Other than the N2reduction, M−S clusters in nature have been found in the conversion of small molecules such as CO2, CO, and H2. With the detailed structures of these native M−S clusters elucidated by recent biochemical studies, we can take steps toward the development of artificial catalysts superior to enzymes and/or those for biologically inaccessible reactions, while another direction is to deeply understand the enzymatic reactions and their relationship between the M−S structures. Here we review the progress in the reaction studies on synthetic M−S clusters, focusing on their utility in the activation and transformation of small molecules. The main part of this review has been divided into three sections: i) transformations of N2and related small molecules, ii) reduction of CO2, and iii) transformations of organic small molecules. Remarkable recent progress includes the development of catalytic N2-silylation toward N(SiMe3)3and CO2reduction toward C1–C4hydrocarbons. Tandem reduction andN-methylation of nitroarenes have also been accomplished in the last decade. Through the review process, the development of catalytic reactions by M−S clusters was found to be still challenging. Collaborative works among chemists who can synthesize M−S clusters, those who are skilled in developing homogeneous catalytic reactions, those having spectroscopic techniques, and theoretical chemists may provide new insights into this field.
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