Well-Defined Low-Valent Cobalt Complexes in Catalysis: An Overview

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 highvalent 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 transitionmetal 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.

Advanced Catalytic Syntheses of 1,3-Oxazine Derivatives via Electrophilic Substitution Using Mono- and Bimetallic Phosphate Catalysts: Co₃(PO 4 ) 2 and CoCa 3 (HPO 4 )(PO 4 ) 2 (OH)

“…Indeed, cobalt presents great versatility and high catalytic activity, which makes it an element of choice for many chemical reactions. Cobalt complexes are often used because of their ability to facilitate various types of organic transformations, such as hydrogenation, oxidation, and coupling reactions [35] , [36]. Additionally, cobalt-modi ed phosphate can provide better stability and increased selectivity in catalytic reactions, contributing to higher yields and more sustainable processes [37].…”