Trapping of a Highly Reactive Oxoiron(IV) Complex in the Catalytic Epoxidation of Olefins by Hydrogen Peroxide
- 주제(키워드) bioinorganic chemistry , catalysis , nonheme oxoiron intermediates , regioselectivity , stereoselective epoxidation
- 주제(기타) Chemistry, Multidisciplinary
- 설명문(일반) [Engelmann, Xenia; Corona, Teresa; Warm, Katrin; Ray, Kallol] Humboldt Univ, Dept Chem, Brook Taylor Str 2, D-12489 Berlin, Germany; [Malik, Deesha D.; Nam, Wonwoo] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 120750, South Korea; [Farquhar, Erik R.] Brookhaven Natl Lab, Case Ctr Synchrotron Biosci, NSLS 2, Upton, NY 11973 USA; [Swart, Marcel] ICREA, Pg Lluis Companys 23, Barcelona 08010, Spain; [Swart, Marcel] Univ Girona, IQCC, Campus Montilivi, Girona 17003, Spain
- 등재 SCIE, SCOPUS
- 발행기관 WILEY-V C H VERLAG GMBH
- 발행년도 2019
- URI http://www.dcollection.net/handler/ewha/000000159687
- 본문언어 영어
- Published As http://dx.doi.org/10.1002/anie.201812758
- PubMed https://pubmed.ncbi.nlm.nih.gov/30663826
초록/요약
The generation of a nonheme oxoiron(IV) intermediate, [(cyclam)Fe-IV(O) (CH3CN)](2+) (2; cyclam=1,4,8,11-tetraazacyclotetradecane), is reported in the reactions of [(cyclam)Fe-II](2+) with aqueous hydrogen peroxide (H2O2) or a soluble iodosylbenzene (sPhIO) as a rare example of an oxoiron(IV) species that shows a preference for epoxidation over allylic oxidation in the oxidation of cyclohexene. Complex 2 is kinetically and catalytically competent to perform the epoxidation of olefins with high stereo- and regioselectivity. More importantly, 2 is likely to be the reactive intermediate involved in the catalytic epoxidation of olefins by [(cyclam)-Fe-II](2+) and H2O2. In spite of the predominance of the oxoiron(IV) cores in biology, the present study is a rare example of high-yield isolation and spectroscopic characterization of a catalytically relevant oxoiron(IV) intermediate in chemical oxidation reactions.
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