Mechanistic Aspects of Cobalt–Oxo Cubane Clusters in Oxidation Chemistry,Journal of the American Chemical Society

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Mechanistic Aspects of Cobalt–Oxo Cubane Clusters in Oxidation Chemistry
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2022-01-21 , DOI: 10.1021/jacs.1c11445
Jaruwan Amtawong _{1,

2} , Andy I Nguyen ₃ , T Don Tilley _{1,

2}

Affiliation

Cobalt oxides are recognized as one of the most efficient earth-abundant catalysts for challenging oxidation chemistry, with substrates ranging from water to organic compounds. In these oxidations, cobalt–oxo species with formal oxidation states greater than 3 are commonly invoked as reactive intermediates. However, there is a dearth of mechanistic information regarding how these high-valent cobalt catalysts operate. This Perspective describes how the study of molecular cobalt oxo clusters, with an emphasis on [Co₄O₄] oxo cubane complexes, has helped to shed light on the operative mechanisms of cobalt-catalyzed oxidation reactions. Implications for high-valent Co^IV–oxo and Co^V–oxo intermediates and remaining mechanistic questions concerning how these intermediates mediate O–O bond formation are also discussed. Furthermore, structural modifications of these oxo cubane clusters (i.e., incorporation of heteroatoms and modulation of ligands) have provided insight into multimetallic cooperativity, but the influence of such metal–metal interactions on oxidation activity remains to be explored. A more detailed understanding of these structure–activity relationships may enable fine-tuning of reactivity and stability of synthetic multimetallic catalysts for energy storage and challenging organic transformations.

中文翻译：

Cobalt-Oxo Cubane 簇在氧化化学中的机理方面

钴氧化物被认为是用于具有挑战性的氧化化学的最有效的地球丰富的催化剂之一，其底物范围从水到有机化合物。在这些氧化反应中，形式氧化态大于 3 的钴-氧化合物通常被用作反应性中间体。然而，关于这些高价钴催化剂如何运作的机械信息匮乏。该观点描述了分子钴氧簇的研究，重点是 [Co ₄ O ₄ ] 氧代立方烷配合物，如何有助于阐明钴催化氧化反应的操作机制。对高价 Co ^IV –oxo 和 Co ^V的影响还讨论了 -oxo 中间体和有关这些中间体如何介导 O-O 键形成的剩余机制问题。此外，这些氧合立方烷簇的结构修饰（即杂原子的掺入和配体的调节）提供了对多金属协同性的深入了解，但这种金属-金属相互作用对氧化活性的影响仍有待探索。对这些结构-活性关系的更详细了解可能有助于微调用于储能和具有挑战性的有机转化的合成多金属催化剂的反应性和稳定性。

更新日期：2022-02-02

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