Author: ["Dong Wang","Erik R. Farquhar","Audria Stubna","Eckard Münck","Lawrence Que Jr"]
CITE.CC academic search helps you expand the influence of your papers.
Abstract
The controlled cleavage of strong C–H bonds such as those of methane poses a significant and industrially important challenge for chemists. In nature, methane is oxidized to methanol by soluble methane monooxygenase via a diiron(iv) intermediate called Q. However, the only two reported diiron(iv) complexes have activities towards C–H bonds that fall far short of the activity of this biological catalyst. In this paper, we model the chemistry of MMO-Q by generating an oxo-bridged diiron(iv) complex by electrochemical oxidation. This species is a more effective oxidant. It can attack C–H bonds as strong as 100 kcal mol−1 and reacts with cyclohexane 100- to 1,000-fold faster than mononuclear FeIV=O complexes of closely related ligands. Strikingly, this species can also cleave the strong O–H bonds of methanol and t-butanol instead of their weaker C–H bonds, representing the first example of O–H bond activation for iron complexes. Carbon–hydrogen bonds are strong and stable, rarely succumbing to the activation attempts of chemists. Certain bacteria are able to metabolize methane using a diiron-centred enzyme, but synthetic analogues have had much less reactivity. Now, an oxo-bridged diiron complex has been shown to have extremely high activity towards C–H bonds. Cite this article
Wang, D., Farquhar, E., Stubna, A. et al. A diiron(iv) complex that cleaves strong C–H and O–H bonds. Nature Chem 1, 145–150 (2009). https://doi.org/10.1038/nchem.162 