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首页> 外文期刊>Coordination chemistry reviews >Metal dithiolene complexes in olefin addition and purification, small molecule adsorption, H_2 evolution and CO_2 reduction
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Metal dithiolene complexes in olefin addition and purification, small molecule adsorption, H_2 evolution and CO_2 reduction

机译：烯烃的金属二硫胺配合物加入和纯化，小分子吸附，H_2进化和CO_2还原

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The transition metal dithiolene complexes bearing unusual electronic and redox non-innocent ligands hold a wide range of applications in the fields of optical materials chemistry, bioinorganic chemistry, electro- or photocatalytic chemistry and reduction chemistry. In this review, we mainly focus on experimental and theoretical works of metal dithiolene complexes and their applications in olefin addition/purification, toxic gas adsorption, H-2 evolution, and CO2 reduction. The coordination of non-innocent dithiolene ligands on transition metal centers give different oxidative state of metals, thus making the reductive character of sulfurs more obvious. And the p orbitals of sulfurs contribute more to the frontier molecular orbitals of metal dithiolene complexes, making the complexes react with olefins on sulfurs rather than metals. The reversable addition of olefins to these ligands could also be achieved, thus releasing olefins to finish the olefin purification process. In this case, metal dithiolenes are facilitating ligand-centered (S) reactivity towards olefin which makes olefin separation easier. Also, metal dithiolene based MOFs are very sophisticated and promising in the term of reduction ability and particular affinity to small molecules. Moreover, to realize a sustainable energy future, electro and photocatalytic manufacturing of H-2 is essential. Here we will also discuss the electro and photocatalyzed proton reductions into H-2 by using metal dithiolene as catalysts in aqueous and weak acetic media. Due to the non-innocent character of dithiolene ligands, the reductive potential of metal dithiolene complexes is usually low, which allows the reduction of CO2 to generate formic acid or CO. In these aspects, many homogeneous and heterogeneous metal dithiolene complexes and related reactions are addressed in this review. (C) 2020 Published by Elsevier B.V.
机译：轴承不寻常的电子和氧化还原非无辜配体的过渡金属二硫胺配合物在光学材料化学，生物碱性化学，电催化化学和还原化学领域拥有广泛的应用。在本综述中，我们主要专注于金属二硫代乙烯配合物的实验和理论作品及其在烯烃添加/纯化，有毒气体吸附，H-2进化和CO 2中的应用。过渡金属中心对非无辜二硫烯配体的配位给出了不同的金属氧化状态，从而使硫磺的还原性能更加明显。硫磺的P轨道促进了金属二硫络合物的前沿分子轨道，使得复合物与硫磺上的烯烃反应而不是金属。还可以实现可逆添加烯烃与这些配体的加法，从而释放烯烃以完成烯烃净化过程。在这种情况下，金属二苯醚促进与烯烃的配体中心反应性，这使烯烃分离更容易。而且，金属金属二硫代乙烯基的MOF是非常复杂的，并且在还原能力和对小分子的特定亲和力的术语中具有非常复杂的。此外，为了实现可持续的能源未来，H-2的电催化和光催化制造至关重要。在这里，我们还将通过在水性和弱醋介质中使用金属二硫代乙烯作为催化剂将电极和光催化的质子减少到H-2中。由于二硫胺配体的非无辜特征，金属二硫胺配合物的还原电位通常是低的，这允许减少CO 2以产生甲酸或CO。在这些方面，许多均匀和异质的金属二硫胺络合物和相关反应是在本次审查中解决了。 （c）2020由elsevier b.v发布。

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