A mononuclear non-heme high-spin iron(III)-hydroperoxo complex as an active oxidant in sulfoxidation reactions

Yun Mi Kim; Kyung Bin Cho; Jaeheung Cho; Binju Wang; Chunsen Li; Sason Shaik; Wonwoo Nam

doi:10.1021/ja404152q

A mononuclear non-heme high-spin iron(III)-hydroperoxo complex as an active oxidant in sulfoxidation reactions

Yun Mi Kim
, Kyung Bin Cho
, Jaeheung Cho
, Binju Wang
, Chunsen Li
, Sason Shaik^*
, Wonwoo Nam

^*Corresponding author for this work

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

77 Scopus citations

Abstract

We report the first direct experimental evidence showing that a high-spin iron(III)-hydroperoxo complex bearing an N-methylated cyclam ligand can oxidize thioanisoles. DFT calculations showed that the reaction pathway involves heterolytic O-O bond cleavage and that the choice of the heterolytic pathway versus the homolytic pathway is dependent on the spin state and the number of electrons in the d_xz orbital of the Fe^III-OOH species.

Original language	English
Pages (from-to)	8838-8841
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	135
Issue number	24
DOIs	https://doi.org/10.1021/ja404152q
State	Published - 19 Jun 2013

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abstract = "We report the first direct experimental evidence showing that a high-spin iron(III)-hydroperoxo complex bearing an N-methylated cyclam ligand can oxidize thioanisoles. DFT calculations showed that the reaction pathway involves heterolytic O-O bond cleavage and that the choice of the heterolytic pathway versus the homolytic pathway is dependent on the spin state and the number of electrons in the dxz orbital of the FeIII-OOH species.",

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AU - Kim, Yun Mi

AU - Cho, Kyung Bin

AU - Cho, Jaeheung

AU - Wang, Binju

AU - Li, Chunsen

AU - Shaik, Sason

AU - Nam, Wonwoo

PY - 2013/6/19

Y1 - 2013/6/19

N2 - We report the first direct experimental evidence showing that a high-spin iron(III)-hydroperoxo complex bearing an N-methylated cyclam ligand can oxidize thioanisoles. DFT calculations showed that the reaction pathway involves heterolytic O-O bond cleavage and that the choice of the heterolytic pathway versus the homolytic pathway is dependent on the spin state and the number of electrons in the dxz orbital of the FeIII-OOH species.

AB - We report the first direct experimental evidence showing that a high-spin iron(III)-hydroperoxo complex bearing an N-methylated cyclam ligand can oxidize thioanisoles. DFT calculations showed that the reaction pathway involves heterolytic O-O bond cleavage and that the choice of the heterolytic pathway versus the homolytic pathway is dependent on the spin state and the number of electrons in the dxz orbital of the FeIII-OOH species.

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DO - 10.1021/ja404152q

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JF - Journal of the American Chemical Society

IS - 24

ER -

A mononuclear non-heme high-spin iron(III)-hydroperoxo complex as an active oxidant in sulfoxidation reactions

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