Nonheme mono- and dinuclear iron complexes in bio-inspired CH and CC bond hydroxylation reactions: Mechanistic insight

• Published in: Inorganica Chimica Acta Vol. 523
• Main Authors: Shteinman, Albert A., Mitra, Mainak
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.08.2021
• Subjects: C[sbnd]H activation; Catalysis; Dihydroxylation; High-valent; Iron mono- and dioxygenases; Iron-oxo; Nonheme; CH activation; High-valent; Iron mono- and dioxygenases; Dihydroxylation; Catalysis; Iron-oxo; Nonheme
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/j.ica.2021.120388

This review focuses on the significant achievements in the stereospecific hydroxylation of CH and CC bonds of hydrocarbons by mono- and dinuclear iron complexes comprising of different N- and/or O-donor ligands over past three decades and addresses the future scopes in this diversified field. A deep insight into the mechanism of stereospecific hydroxylation reactions catalyzed by these iron complexes has been provided. These reactions essentially proceed via the intermediacy of highly reactive Fe(IV)-oxo and/or Fe(V)-oxo species. However, the overall catalytic outcomes are found to be largely influenced by several other factors such as the chemo-, regio-, and stereoselectivity imposed by the reactive intermediates as well as by the substrates involved, the nature of additives, catalytic reaction conditions etc. [Display omitted] •Nonheme iron oxygenases perform diverse but biologically relevant oxidation reactions.•Mono- and di iron complexes in biomimetic oxidation catalysis have been summarized.•Mechanistic insight highlights the role of key oxidants in the CH hydroxylation reactions. The selective catalytic functionalization of hydrocarbons under mild conditions is a subject of considerable current interest. While selective oxidations of CH bonds remain a challenging task to the synthetic chemists, Nature provides several successful solutions to this by utilizing remarkably efficient biocatalysts, namely the oxygenases. Iron-containing oxygenases with heme or nonheme active sites participate in biologically important oxidative transformation reactions by dioxygen activation. The transient high-valent iron-oxo species thus generated are proposed to be the key reactive intermediates in the oxidation reactions and have been detected in several occasions. Inspired by the Nature, rational design of synthetic analogues of iron oxygenases paves the way for the development of efficient catalysts for selective CH bond oxidation. This review focuses on the significant advances made in the catalytic oxidations of hydrocarbons by different nonheme mono- and dinuclear iron complexes over past three decades with a highlight on the mechanistic aspects and addresses the forthcoming challenges in this field.