Abstract
C−H oxidation is catalyzed by a high-spin ferrous dimer, [(L1)2Fe2(CH3CN)2](PF6)4 (1), that offers two identical functional sites, separated by > 7 Å. The complex provides a unique contrast to both mononuclear and binuclear non-heme enzyme active sites as well as biomimetic complexes. The oxidative activity of 1 was examined using a range of substrates (cyclohexene, 9,10-dihydroanthracene, xanthene, triphenylmethane, triphenylphosphine, and cyclohexane) and PhIO as an oxidant. The studies establish the O-atom transfer and H-atom abstraction ability of the diiron complex. We further probe the energetics of cyclohexene oxidation by 1 and derive putative mechanisms for the pathways of allylic alcohol and epoxide formation using density functional theory (DFT) calculations. The DFT calculations indicate that the oxidation reactions proceed via a FeIV=O species in the triplet state, and that both iron centers can act independently of each other. The combined results provide insight into hydrocarbon oxidation by non-coupled binuclear systems.
Original language | English |
---|---|
Pages (from-to) | 1602-1608 |
Number of pages | 7 |
Journal | ChemistrySelect |
Volume | 3 |
Issue number | 5 |
DOIs | |
State | Published - 7 Feb 2018 |
Keywords
- DFT
- diiron
- hydrocarbon oxidation
- iron-oxo
- non-heme