C-H bond cleavage by bioinspired nonheme oxoiron(IV) complexes, including hydroxylation of n-butane

Scott T. Kleespies, Williamson N Oloo, Anusree Mukherjee, Larry Que

Research output: Contribution to journalReview article

32 Scopus citations

Abstract

The development of efficient and selective hydrocarbon oxidation processes with low environmental impact remains a major challenge of the 21st century because of the strong and apolar nature of the C-H bond. Naturally occurring iron-containing metalloenzymes can, however, selectively functionalize strong C-H bonds on substrates under mild and environmentally benign conditions. The key oxidant in a number of these transformations is postulated to possess an S = 2 FeIV - O unit in a nonheme ligand environment. This oxidant has been trapped and spectroscopically characterized and its reactivity toward C-H bonds demonstrated for several nonheme iron enzyme classes. In order to obtain insight into the structure-activity relationships of these reactive intermediates, over 60 synthetic nonheme FeIV(O) complexes have been prepared in various laboratories and their reactivities investigated. This Forum Article summarizes the current status of efforts in the characterization of the C-H bond cleavage reactivity of synthetic FeIV(O) complexes and provides a snapshot of the current understanding of factors that control this reactivity, such as the properties of the supporting ligands and the spin state of the iron center. In addition, new results on the oxidation of strong C-H bonds such as those of cyclohexane and n-butane by a putative S = 2 synthetic FeIV(O) species that is generated in situ using dioxygen at ambient conditions are presented.

Original languageEnglish (US)
Pages (from-to)5053-5064
Number of pages12
JournalInorganic Chemistry
Volume54
Issue number11
DOIs
StatePublished - Jun 1 2015

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