On the Upper Limits of Oxidation States in Chemistry

Shu Xian Hu; Wan Lu Li; Jun Bo Lu; Junwei Lucas Bao; Haoyu S. Yu; Donald G. Truhlar; John K. Gibson; Joaquim Marçalo; Mingfei Zhou; Sebastian Riedel; W. H.Eugen Schwarz; Jun Li

doi:10.1002/anie.201711450

On the Upper Limits of Oxidation States in Chemistry

Shu Xian Hu, Wan Lu Li, Jun Bo Lu, Junwei Lucas Bao, Haoyu S. Yu, Donald G. Truhlar, John K. Gibson, Joaquim Marçalo, Mingfei Zhou, Sebastian Riedel, W. H.Eugen Schwarz, Jun Li

Chemistry (Twin Cities)

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

41 Scopus citations

Abstract

The concept of oxidation state (OS) is based on the concept of Lewis electron pairs, in which the bonding electrons are assigned to the more electronegative element. This approach is useful for keeping track of the electrons, predicting chemical trends, and guiding syntheses. Experimental and quantum-chemical results reveal a limit near +8 for the highest OS in stable neutral chemical substances under ambient conditions. OS=+9 was observed for the isolated [IrO₄]⁺ cation in vacuum. The prediction of OS=+10 for isolated [PtO₄]²⁺ cations is confirmed computationally for low temperatures only, but hasn't yet been experimentally verified. For high OS species, oxidation of the ligands, for example, of O⁻² with formation of ^.O⁻¹ and O−O bonds, and partial reduction of the metal center may be favorable, possibly leading to non-Lewis type structures.

Original language	English (US)
Pages (from-to)	3242-3245
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	12
DOIs	https://doi.org/10.1002/anie.201711450
State	Published - Mar 12 2018

Bibliographical note

Funding Information:
We thank Professors Jeremy Harvey and Martin Kaupp for illuminating discussions. W.H.E.S. thanks the Theoretical Chemistry Center of THU for hospitality and support. J.L. acknowledges the NSFC (grant nos. 21590792, 21433005, and 91426302) for financial support. S.X.H. acknowledges the NSFC (grant no. 21701006), the Foundation of the President of the Chinese Academy of Engineering Physics (grant no. YZJJSQ2017072), and the NASF (grant no. U1530401) for support. M.Z. was supported by the NSFC (grant no. 21433005). J.K.G. was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Element Chemistry Program at Lawrence Berkeley National Laboratory under Contract DE-AC02-05CH1123. The work in Minnesota was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0015997. J.M. thanks the FundaÅ¼o para a CiÞncia e a Tecnologia (Portugal) for financial support through project UID/Multi/04349/2013 and RNEM – Portuguese Mass Spectrometry Network.

Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

bonding theory
computational chemistry
oxidation states
oxides
transition metals

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10.1002/anie.201711450

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title = "On the Upper Limits of Oxidation States in Chemistry",

abstract = "The concept of oxidation state (OS) is based on the concept of Lewis electron pairs, in which the bonding electrons are assigned to the more electronegative element. This approach is useful for keeping track of the electrons, predicting chemical trends, and guiding syntheses. Experimental and quantum-chemical results reveal a limit near +8 for the highest OS in stable neutral chemical substances under ambient conditions. OS=+9 was observed for the isolated [IrO4]+ cation in vacuum. The prediction of OS=+10 for isolated [PtO4]2+ cations is confirmed computationally for low temperatures only, but hasn't yet been experimentally verified. For high OS species, oxidation of the ligands, for example, of O−2 with formation of .O−1 and O−O bonds, and partial reduction of the metal center may be favorable, possibly leading to non-Lewis type structures.",

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author = "Hu, {Shu Xian} and Li, {Wan Lu} and Lu, {Jun Bo} and Bao, {Junwei Lucas} and Yu, {Haoyu S.} and Truhlar, {Donald G.} and Gibson, {John K.} and Joaquim Mar{\c c}alo and Mingfei Zhou and Sebastian Riedel and Schwarz, {W. H.Eugen} and Jun Li",

note = "Funding Information: We thank Professors Jeremy Harvey and Martin Kaupp for illuminating discussions. W.H.E.S. thanks the Theoretical Chemistry Center of THU for hospitality and support. J.L. acknowledges the NSFC (grant nos. 21590792, 21433005, and 91426302) for financial support. S.X.H. acknowledges the NSFC (grant no. 21701006), the Foundation of the President of the Chinese Academy of Engineering Physics (grant no. YZJJSQ2017072), and the NASF (grant no. U1530401) for support. M.Z. was supported by the NSFC (grant no. 21433005). J.K.G. was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Element Chemistry Program at Lawrence Berkeley National Laboratory under Contract DE-AC02-05CH1123. The work in Minnesota was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0015997. J.M. thanks the Funda{\AA}¼o para a Ci{\TH}ncia e a Tecnologia (Portugal) for financial support through project UID/Multi/04349/2013 and RNEM – Portuguese Mass Spectrometry Network. Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Li, Wan Lu

AU - Lu, Jun Bo

AU - Bao, Junwei Lucas

AU - Yu, Haoyu S.

AU - Truhlar, Donald G.

AU - Gibson, John K.

AU - Marçalo, Joaquim

AU - Zhou, Mingfei

AU - Riedel, Sebastian

AU - Schwarz, W. H.Eugen

AU - Li, Jun

N1 - Funding Information: We thank Professors Jeremy Harvey and Martin Kaupp for illuminating discussions. W.H.E.S. thanks the Theoretical Chemistry Center of THU for hospitality and support. J.L. acknowledges the NSFC (grant nos. 21590792, 21433005, and 91426302) for financial support. S.X.H. acknowledges the NSFC (grant no. 21701006), the Foundation of the President of the Chinese Academy of Engineering Physics (grant no. YZJJSQ2017072), and the NASF (grant no. U1530401) for support. M.Z. was supported by the NSFC (grant no. 21433005). J.K.G. was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Element Chemistry Program at Lawrence Berkeley National Laboratory under Contract DE-AC02-05CH1123. The work in Minnesota was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0015997. J.M. thanks the FundaÅ¼o para a CiÞncia e a Tecnologia (Portugal) for financial support through project UID/Multi/04349/2013 and RNEM – Portuguese Mass Spectrometry Network. Publisher Copyright: © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2018/3/12

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N2 - The concept of oxidation state (OS) is based on the concept of Lewis electron pairs, in which the bonding electrons are assigned to the more electronegative element. This approach is useful for keeping track of the electrons, predicting chemical trends, and guiding syntheses. Experimental and quantum-chemical results reveal a limit near +8 for the highest OS in stable neutral chemical substances under ambient conditions. OS=+9 was observed for the isolated [IrO4]+ cation in vacuum. The prediction of OS=+10 for isolated [PtO4]2+ cations is confirmed computationally for low temperatures only, but hasn't yet been experimentally verified. For high OS species, oxidation of the ligands, for example, of O−2 with formation of .O−1 and O−O bonds, and partial reduction of the metal center may be favorable, possibly leading to non-Lewis type structures.

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KW - bonding theory

KW - computational chemistry

KW - oxidation states

KW - oxides

KW - transition metals

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ER -

On the Upper Limits of Oxidation States in Chemistry

Abstract

Bibliographical note

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