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, H₂ 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 H₂ is essential. Here we will also discuss the electro and photocatalyzed proton reductions into H₂ 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.

带有不寻常的电子和氧化还原非纯配体的过渡金属二硫辛烯络合物在光学材料化学，生物无机化学，电催化或光催化化学和还原化学领域具有广泛的应用。在这篇综述中，我们主要关注金属二硫杂环戊烯配合物的实验和理论工作及其在烯烃添加/纯化，有毒气体吸附，H ₂析出和CO ₂还原中的应用。非纯二硫代烯配体在过渡金属中心的配位会赋予金属不同的氧化态，从而使硫的还原特性更加明显。和p硫的轨道对金属二硫杂环戊烯配合物的前沿分子轨道的贡献更大，使配合物与硫而不是金属上的烯烃反应。还可以实现烯烃向这些配体的可逆加成，从而释放烯烃以完成烯烃纯化过程。在这种情况下，金属二硫代烯烃有助于促进对烯烃的以配体为中心的（S）反应性，这使烯烃的分离更加容易。同样，基于金属二硫烯基的MOF在还原能力和对小分子的特殊亲和力方面非常复杂并且很有前途。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，我们还将讨论电和光催化质子还原为H ₂通过在水和弱乙酸介质中使用金属二硫辛烯作为催化剂。由于二硫代烯配体的非清纯特性，金属二硫代烯配合物的还原电势通常较低，这使得CO ₂还原可生成甲酸或CO。在这些方面，许多均相和非均质的金属二硫代烯配合物及相关反应在这篇评论中得到解决。