Cassandre C. Bories*, Alexandre Sodreau, Marion Barbazanges and Marc Petit*,
{"title":"Well-Defined Low-Valent Cobalt Complexes in Catalysis: An Overview","authors":"Cassandre C. Bories*, Alexandre Sodreau, Marion Barbazanges and Marc Petit*, ","doi":"10.1021/acs.organomet.4c00054","DOIUrl":null,"url":null,"abstract":"<p >For decades, transition-metal catalysts based on noble metals have proven to be highly efficient for a wide range of organic transformations. However, due to their low abundance and highly volatile price the use of such metals is now critical for the economy. Thus, the use of more sustainable alternatives is mandatory and the more abundant first-row transition metals are becoming interesting challengers. Among them low-valent 3d transition metals appeared as the best candidates, as they are intrinsically more reactive than high-valent ones. However, this reactivity implies that these complexes are often generated <i>in situ</i>, putting further away the aspect of atom economy and low waste. To circumvent this and to get more insight on the mechanism of reaction, the concept of well-defined complexes has emerged. In this area, due to its historic development and the trouble associated with the preparation of other well-defined 3d transition-metal complexes, cobalt appears as an important player. In this review, after a definition of what is a low-valent complex and the presentation of the concept of a well-defined (pre)catalyst also known as the “single-component” strategy we will report the syntheses and applications in catalysis of low-valent well-defined cobalt complexes classified by their oxidation state and ligand environment.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":null,"pages":null},"PeriodicalIF":2.5000,"publicationDate":"2024-04-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.4c00054","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
For decades, transition-metal catalysts based on noble metals have proven to be highly efficient for a wide range of organic transformations. However, due to their low abundance and highly volatile price the use of such metals is now critical for the economy. Thus, the use of more sustainable alternatives is mandatory and the more abundant first-row transition metals are becoming interesting challengers. Among them low-valent 3d transition metals appeared as the best candidates, as they are intrinsically more reactive than high-valent ones. However, this reactivity implies that these complexes are often generated in situ, putting further away the aspect of atom economy and low waste. To circumvent this and to get more insight on the mechanism of reaction, the concept of well-defined complexes has emerged. In this area, due to its historic development and the trouble associated with the preparation of other well-defined 3d transition-metal complexes, cobalt appears as an important player. In this review, after a definition of what is a low-valent complex and the presentation of the concept of a well-defined (pre)catalyst also known as the “single-component” strategy we will report the syntheses and applications in catalysis of low-valent well-defined cobalt complexes classified by their oxidation state and ligand environment.
几十年来,以贵金属为基础的过渡金属催化剂已被证明可高效地进行各种有机转化。然而,由于其储量低且价格极不稳定,这类金属的使用现在对经济至关重要。因此,必须使用更具可持续性的替代品,而储量更丰富的第一排过渡金属正成为令人感兴趣的挑战者。其中,低价 3d 过渡金属似乎是最佳候选者,因为与高价金属相比,它们本质上更具反应性。然而,这种反应性意味着这些络合物通常是在原位生成的,从而进一步降低了原子经济性和低废物方面的要求。为了避免这种情况,并更深入地了解反应机理,出现了定义明确的络合物概念。在这一领域,由于钴的历史发展以及制备其他定义明确的 3d 过渡金属配合物的麻烦,钴显得尤为重要。在本综述中,在定义了什么是低价配合物以及介绍了定义明确的(预)催化剂(也称为 "单组分 "策略)的概念之后,我们将报告按氧化态和配体环境分类的低价定义明确的钴配合物的合成及其在催化中的应用。
期刊介绍:
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.