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Issue 12, 2017
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A theoretical study on oxidative cleavage of olefins to carbonyls catalysed by Fe(III)-PyBisulidine

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Abstract

An environmentally friendly new protocol for the selective aerobic cleavage of styrene to carbonyl compounds using the Fe(III)-PyBisulidine catalyst has been reported recently. The catalyst features several unusual characteristics, such as its high efficiency lies on the ferric center instead of ferrous used by most iron-containing oxygenases and the catalyst specifically oxidizes phenyl-substituted olefins but exhibits no activity on nonconjugated olefins. Herein, we have investigated the mechanism of the oxidative cleavage reaction catalyzed by Fe(III)-PyBisulidine at the quantum chemistry level. Our computational study shows that the catalyst uses a dioxygen ligation mechanism to activate dioxygen to receive one electron from olefin, which triggers the oxidative cleavage reaction. Our study rationalizes that the Fe(II)-PyBisulidine catalyst is inactivated because ferrous is unable to raise the oxidizing ability of dioxygen. The exclusive oxidative cleavage of the phenyl-substituted olefin mainly results from the stability of the carbon cation, the orbital symmetry between the conjugated olefin and dioxygen, as well as a lower energy level of HOMO in conjugated olefin.

Graphical abstract: A theoretical study on oxidative cleavage of olefins to carbonyls catalysed by Fe(iii)-PyBisulidine

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Publication details

The article was received on 19 Jan 2017, accepted on 17 Feb 2017 and first published on 20 Feb 2017


Article type: Paper
DOI: 10.1039/C7DT00229G
Citation: Dalton Trans., 2017,46, 3825-3832
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    A theoretical study on oxidative cleavage of olefins to carbonyls catalysed by Fe(III)-PyBisulidine

    Y. Jiang, X. Zhang, Q. Mao, H. Tan, X. Li, G. Chen and Z. Jia, Dalton Trans., 2017, 46, 3825
    DOI: 10.1039/C7DT00229G

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