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Mechanistic elucidation of C-H oxidation by electron rich non-heme iron(IV)-oxo at room temperature

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Title Mechanistic elucidation of C-H oxidation by electron rich non-heme iron(IV)-oxo at room temperature
 
Creator RANA, S
DEY, A
MAITI, D
 
Subject IRON-OXO COMPLEXES
HYDROGEN-ATOM ABSTRACTION
HIGH-VALENT IRON
OXOIRON(IV) COMPLEX
BOND ACTIVATION
OXYGENATION REACTIONS
(FEO)-O-IV COMPLEXES
ALKANE HYDROXYLATION
REBOUND MECHANISM
REACTIVITY
 
Description Non-heme iron(IV)-oxo species form iron(III) intermediates during hydrogen atom abstraction (HAA) from the C-H bond. While synthesizing a room temperature stable, electron rich, non-heme iron(IV)-oxo compound, we obtained iron(III)-hydroxide, iron(III)-alkoxide and hydroxylated-substrate-bound iron(II) as the detectable intermediates. The present study revealed that a radical rebound pathway was operative for benzylic C-H oxidation of ethylbenzene and cumene. A dissociative pathway for cyclohexane oxidation was established based on UV-vis and radical trap experiments. Interestingly, experimental evidence including O-18 labeling and mechanistic study suggested an electron transfer mechanism to be operative during C-H oxidation of alcohols (e.g. benzyl alcohol and cyclobutanol). The present report, therefore, unveils non-heme iron(IV)-oxo promoted substrate-dependent C-H oxidation pathways which are of synthetic as well as biological significance.
 
Publisher ROYAL SOC CHEMISTRY
 
Date 2016-01-15T07:01:14Z
2016-01-15T07:01:14Z
2015
 
Type Article
 
Identifier CHEMICAL COMMUNICATIONS, 51(77)14469-14472
1359-7345
1364-548X
http://dx.doi.org/10.1039/c5cc04803f
http://dspace.library.iitb.ac.in/jspui/handle/100/17997
 
Language en