Electron Transfer Oxidation of Benzene and Aerobic Oxidation to Phenol

Bidyut Bikash Sarma; Raanan Carmieli; Alberto Collauto; Irena Efremenko; Jan M.L. Martin; Ronny Neumann

doi:10.1021/acscatal.6b02083

Electron Transfer Oxidation of Benzene and Aerobic Oxidation to Phenol

Bidyut Bikash Sarma, Raanan Carmieli, Alberto Collauto, Irena Efremenko, Jan M.L. Martin, Ronny Neumann^*

^*Corresponding author for this work

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

48 Scopus citations

Abstract

The activation of very strong C-H bonds, such as those found in benzene, is important also in the quest for new routes for its functionalization. Using the H₅PV₂Mo₁₀O₄₀ polyoxometalate as an electron transfer oxidant in >50% aqueous H₂SO₄ as solvent, the formation of a benzene radicaloid species at RT as probed by visible spectroscopy and by EPR spectroscopy recorded at X-band and W-band, including ELDOR-detected NMR, was verified. The viability of the ET oxidation of benzene is supported by DFT calculations, showing the reaction to be exergonic under these conditions. Furthermore, we show that in the presence of O₂, very selective hydroxylation to phenol took place.

Original language	English
Pages (from-to)	6403-6407
Number of pages	5
Journal	ACS Catalysis
Volume	6
Issue number	10
DOIs	https://doi.org/10.1021/acscatal.6b02083
State	Published - 7 Oct 2016
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

Keywords

EPR
aerobic oxidation
benzene
electron transfer
polyoxometalate

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10.1021/acscatal.6b02083

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abstract = "The activation of very strong C-H bonds, such as those found in benzene, is important also in the quest for new routes for its functionalization. Using the H5PV2Mo10O40 polyoxometalate as an electron transfer oxidant in >50% aqueous H2SO4 as solvent, the formation of a benzene radicaloid species at RT as probed by visible spectroscopy and by EPR spectroscopy recorded at X-band and W-band, including ELDOR-detected NMR, was verified. The viability of the ET oxidation of benzene is supported by DFT calculations, showing the reaction to be exergonic under these conditions. Furthermore, we show that in the presence of O2, very selective hydroxylation to phenol took place.",

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AU - Sarma, Bidyut Bikash

AU - Carmieli, Raanan

AU - Collauto, Alberto

AU - Efremenko, Irena

AU - Martin, Jan M.L.

AU - Neumann, Ronny

PY - 2016/10/7

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AB - The activation of very strong C-H bonds, such as those found in benzene, is important also in the quest for new routes for its functionalization. Using the H5PV2Mo10O40 polyoxometalate as an electron transfer oxidant in >50% aqueous H2SO4 as solvent, the formation of a benzene radicaloid species at RT as probed by visible spectroscopy and by EPR spectroscopy recorded at X-band and W-band, including ELDOR-detected NMR, was verified. The viability of the ET oxidation of benzene is supported by DFT calculations, showing the reaction to be exergonic under these conditions. Furthermore, we show that in the presence of O2, very selective hydroxylation to phenol took place.

KW - EPR

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Electron Transfer Oxidation of Benzene and Aerobic Oxidation to Phenol

Abstract

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