A diiron(iv) complex that cleaves strong C–H and O–H bonds
- 29 March 2009
- journal article
- research article
- Published by Springer Nature in Nature Chemistry
- Vol. 1 (2) , 145-150
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.Keywords
This publication has 38 references indexed in Scilit:
- Axial Ligand Effects on the Geometric and Electronic Structures of Nonheme Oxoiron(IV) ComplexesJournal of the American Chemical Society, 2008
- A synthetic precedent for the [Fe IV 2 (μ-O) 2 ] diamond core proposed for methane monooxygenase intermediate QProceedings of the National Academy of Sciences, 2007
- Axial ligand tuning of a nonheme iron(IV)–oxo unit for hydrogen atom abstractionProceedings of the National Academy of Sciences, 2007
- Spectroscopic and Quantum Chemical Studies on Low-Spin FeIVO Complexes: Fe−O Bonding and Its Contributions to ReactivityJournal of the American Chemical Society, 2007
- Electrochemical Generation of a Nonheme Oxoiron(IV) ComplexInorganic Chemistry, 2006
- Nonheme Oxoiron(IV) Complexes of Tris(2-pyridylmethyl)amine with cis-Monoanionic LigandsInorganic Chemistry, 2006
- Catalytically Active μ-Oxodiiron(IV) Oxidants from Iron(III) and DioxygenJournal of the American Chemical Society, 2005
- Oxygen Economy of Cytochrome P450: What Is the Origin of the Mixed Functionality as a Dehydrogenase−Oxidase Enzyme Compared with Its Normal Function?Journal of the American Chemical Society, 2004
- The Flexible Fe2(μ-O)2 Diamond Core: A Terminal Iron(IV)−Oxo Species Generated from the Oxidation of a Bis(μ-oxo)diiron(III) ComplexJournal of the American Chemical Society, 2000
- Large Kinetic Isotope Effects in Methane Oxidation Catalyzed by Methane Monooxygenase: Evidence for C−H Bond Cleavage in a Reaction Cycle IntermediateBiochemistry, 1996