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Title: On the Upper Limits of Oxidation States in Chemistry

Abstract

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 [IrO 4 ] + cation in vacuum. The prediction of OS =+10 for isolated [PtO 4 ] 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.

Authors:
 [1];  [2];  [3];  [4];  [4]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [7]; ORCiD logo [8]; ORCiD logo [9]; ORCiD logo [2]
+ Show Author Affiliations
  1. Tsinghua Univ., Beijing (China). Key Lab. of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Dept. of Chemistry; Beijing Computer Science Research Center Haidian, Beijing (China)
  2. Tsinghua Univ., Beijing (China). Key Lab. of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Dept. of Chemistry
  3. Tsinghua Univ., Beijing (China). Key Lab. of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Dept. of Chemistry; Univ. of Minnesota, Minneapolis, MN (United States). Minnesota Supercomputing Inst., Chemical Theory Center, Dept. of Chemistry
  4. Univ. of Minnesota, Minneapolis, MN (United States). Minnesota Supercomputing Inst., Chemical Theory Center, Dept. of Chemistry
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  6. Univ. de Lisboa, Bobadela (Portugal). Centro de Ciencias e Tecnologias Nucleares, Inst. Superior Tecnico
  7. Fudan Univ., Shanghai (China). Dept. of Chemistry
  8. Freie Univ. Berlin, Berlin (Germany). Anorganische Chemie, Inst. fur Chemie und Biochemie
  9. Tsinghua Univ., Beijing (China). Key Lab. of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Dept. of Chemistry; Univ. Siegen, Siegen (Germany). Physical and Theoretical Chemistry Lab.
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC)
OSTI Identifier:
1461134
Alternate Identifier(s):
OSTI ID: 1422008
Grant/Contract Number:  
AC02-05CH11231; 21590792; 91426302; 91645203; 2170106; 21433005; U1530401; SC0015997; UID/Multi/04349/2013; AC02-05CH1123
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 12; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; bonding theory; computational chemistry; oxidation states; oxides; transition metals

Citation Formats

Hu, Shu-Xian, Li, Wan-Lu, Lu, Jun-Bo, Bao, Junwei Lucas, Yu, Haoyu S., Truhlar, Donald G., Gibson, John K., Marcalo, Joaquim, Zhou, Mingfei, Riedel, Sebastian, Schwarz, W. H. Eugen, and Li, Jun. On the Upper Limits of Oxidation States in Chemistry. United States: N. p., 2018. Web. doi:10.1002/anie.201711450.
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Hu, Shu-Xian, Li, Wan-Lu, Lu, Jun-Bo, Bao, Junwei Lucas, Yu, Haoyu S., Truhlar, Donald G., Gibson, John K., Marcalo, Joaquim, Zhou, Mingfei, Riedel, Sebastian, Schwarz, W. H. Eugen, & Li, Jun. On the Upper Limits of Oxidation States in Chemistry. United States. https://doi.org/10.1002/anie.201711450
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Hu, Shu-Xian, Li, Wan-Lu, Lu, Jun-Bo, Bao, Junwei Lucas, Yu, Haoyu S., Truhlar, Donald G., Gibson, John K., Marcalo, Joaquim, Zhou, Mingfei, Riedel, Sebastian, Schwarz, W. H. Eugen, and Li, Jun. Mon . "On the Upper Limits of Oxidation States in Chemistry". United States. https://doi.org/10.1002/anie.201711450. https://www.osti.gov/servlets/purl/1461134.
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@article{osti_1461134,
title = {On the Upper Limits of Oxidation States in Chemistry},
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 Marcalo, Joaquim and Zhou, Mingfei and Riedel, Sebastian and Schwarz, W. H. Eugen and Li, Jun},
abstractNote = {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 [IrO 4 ] + cation in vacuum. The prediction of OS =+10 for isolated [PtO 4 ] 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.},
doi = {10.1002/anie.201711450},
journal = {Angewandte Chemie (International Edition)},
number = 12,
volume = 57,
place = {United States},
year = {2018},
month = {2}
}
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https://doi.org/10.1002/anie.201711450
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Cited by: 42 works
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Figures / Tables:

Figure 1 Figure 1: Space-filling calotte models of [Pt∙4O] 2+ (red: O −2 ; green: Pt +q ). Left: Tetrahedral Td-[Pt +10 O −2 4] 2+ . Right: C2v-[O −2 2 Pt +7 (O2) −1 ] 2+ . The O −2 ligands of Td-[PtO4] 2+ are all weakly overlapping. The right (O2)more » ‒1 ligand of the C2v isomer is a superoxide unit.« less
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Works referenced in this record:

Oxidation State 10 Exists
journal, June 2016

Oxidation State, A Long-Standing Issue!
journal, March 2015

Structures of Platinum Oxide Clusters in the Gas Phase
journal, August 2012

  • Kerpal, Christian; Harding, Dan J.; Hermes, Alexander C.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 6
  • DOI: 10.1021/jp3055137

The Origin of the Oxidation-State Concept
journal, September 2007

  • Jensen, William B.
  • Journal of Chemical Education, Vol. 84, Issue 9
  • DOI: 10.1021/ed084p1418

How Much Can Density Functional Approximations (DFA) Fail? The Extreme Case of the FeO 4 Species
journal, March 2016

  • Huang, Wei; Xing, Deng-Hui; Lu, Jun-Bo
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 4
  • DOI: 10.1021/acs.jctc.5b01040

Formation and Characterization of the Iridium Tetroxide Molecule with Iridium in the Oxidation State +VIII
journal, October 2009

  • Gong, Yu; Zhou, Mingfei; Kaupp, Martin
  • Angewandte Chemie International Edition, Vol. 48, Issue 42
  • DOI: 10.1002/anie.200902733

Caesium in high oxidation states and as a p-block element
journal, September 2013

Die formalen Oxidationszahlen des Iridiums reichen nun von −III bis +IX
journal, December 2014

”Developing paradigms of chemical bonding: adaptive natural density partitioning
journal, January 2008

  • Zubarev, Dmitry Yu.; Boldyrev, Alexander I.
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 34
  • DOI: 10.1039/b804083d

PLATINUM HEXAFLUORIDE 1
journal, November 1957

  • Weinstock, Bernard; Claassen, Howard H.; Malm, John G.
  • Journal of the American Chemical Society, Vol. 79, Issue 21
  • DOI: 10.1021/ja01578a073

Cesium's Off-the-Map Valence Orbital
journal, July 2017

  • Goesten, Maarten G.; Rahm, Martin; Bickelhaupt, F. Matthias
  • Angewandte Chemie International Edition, Vol. 56, Issue 33
  • DOI: 10.1002/anie.201704118

Density-functional investigation of bonding in tetrahedral MO4 anions
journal, August 2001

Solid-State 129 Xe and 131 Xe NMR Study of the Perxenate Anion XeO 6 4-
journal, April 2007

  • Forgeron, Michelle A. M.; Wasylishen, Roderick E.; Gerken, Michael
  • Inorganic Chemistry, Vol. 46, Issue 9
  • DOI: 10.1021/ic0624524

On the Highest Oxidation States of Metal Elements in MO 4 Molecules (M = Fe, Ru, Os, Hs, Sm, and Pu)
journal, April 2016

Is rhodium tetroxide in the formal oxidation state VIII stable? a quantum chemical and matrix isolation investigation of rhodium oxides
journal, March 2011

  • Gong, Yu; Zhou, Mingfei; Andrews, Lester
  • Theoretical Chemistry Accounts, Vol. 129, Issue 3-5
  • DOI: 10.1007/s00214-011-0919-7

Specific Chemistry of the Anions: [TaOF 5 ] 2– , [TaF 6 ] − , and [TaF 7 ] 2–
journal, January 2014

  • Lu, Hongcheng; Gautier, Romain; Donakowski, Martin D.
  • Crystal Growth & Design, Vol. 14, Issue 2
  • DOI: 10.1021/cg401710j

On the Extreme Oxidation States of Iridium
journal, May 2015

Analysis of nondynamical correlation in the metal–ligand bond. Pauli repulsion and orbital localization in MnO − 4
journal, September 1990

  • Buijse, Marten A.; Baerends, Evert Jan
  • The Journal of Chemical Physics, Vol. 93, Issue 6
  • DOI: 10.1063/1.458746

Electronic structure of oxygen-related defects in PbWO 4 and CaMoO 4 crystals
journal, December 2001

Hafnium in peralkaline and peraluminous boro-aluminosilicate glass and glass sub-components: a solubility study
journal, October 2003

How Far Can We Go? Quantum-Chemical Investigations of Oxidation State +IX
journal, February 2010

  • Himmel, Daniel; Knapp, Carsten; Patzschke, Michael
  • ChemPhysChem, Vol. 11, Issue 4
  • DOI: 10.1002/cphc.200900910

A Facile Synthesis of Pure O 2 PtF 6 : A Facile Synthesis of Pure O
journal, August 2015

  • Rudel, Stefan S.; Kraus, Florian
  • Zeitschrift für anorganische und allgemeine Chemie, Vol. 641, Issue 14
  • DOI: 10.1002/zaac.201500616

Oxidation State 10 Exists
journal, June 2016

  • Yu, Haoyu S.; Truhlar, Donald G.
  • Angewandte Chemie International Edition, Vol. 55, Issue 31
  • DOI: 10.1002/anie.201604670

Identification of an iridium-containing compound with a formal oxidation state of IX
journal, October 2014

  • Wang, Guanjun; Zhou, Mingfei; Goettel, James T.
  • Nature, Vol. 514, Issue 7523
  • DOI: 10.1038/nature13795

Formation and Characterization of the Iridium Tetroxide Molecule with Iridium in the Oxidation State +VIII
journal, October 2009

Cesium's Off‐the‐Map Valence Orbital
journal, July 2017

  • Goesten, Maarten G.; Rahm, Martin; Bickelhaupt, F. Matthias
  • Angewandte Chemie, Vol. 129, Issue 33
  • DOI: 10.1002/ange.201704118

Principal Components of Ionicity
journal, August 1994

  • Meister, J.; Schwarz, W. H. E.
  • The Journal of Physical Chemistry, Vol. 98, Issue 33
  • DOI: 10.1021/j100084a048

Die Oxidationsstufe, ein Dauerbrenner!
journal, March 2015

From Widely Accepted Concepts in Coordination Chemistry to Inverted Ligand Fields
journal, June 2016

The Formal Oxidation States of Iridium Now Run from −III to +IX
journal, December 2014

  • Pyykkö, Pekka; Xu, Wen-Hua
  • Angewandte Chemie International Edition, Vol. 54, Issue 4
  • DOI: 10.1002/anie.201410615

Infrared Spectra and Density Functional Calculations of MO 2 , MO 3 , (O 2 )MO 2 , MO 4 , MO 2 - (M = Re, Ru, Os) and ReO 3 - , ReO 4 - in Solid Neon and Argon †
journal, April 2000

  • Zhou, Mingfei; Citra, Angelo; Liang, Binyong
  • The Journal of Physical Chemistry A, Vol. 104, Issue 16
  • DOI: 10.1021/jp993026p

Zur Kristallstruktur von O2+MF6? (M = Sb, Ru, Pt, Au)
journal, June 1996

  • Graudejus, O.; M�ller, B. G.
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 622, Issue 6
  • DOI: 10.1002/zaac.19966220623

Beyond state I
journal, September 2013

  • Riedel, Sebastian; Schwerdtfeger, Peter
  • Nature Chemistry, Vol. 5, Issue 10
  • DOI: 10.1038/nchem.1767
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    • Steen, Jelte S.; Knizia, Gerald; Klein, Johannes E. M. N.
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    • DOI: 10.1002/ange.201906658

    An Objective Alternative to IUPAC's Approach To Assign Oxidation States
    journal, August 2018

    • Postils, Verònica; Delgado‐Alonso, Carlos; Luis, Josep M.
    • Angewandte Chemie International Edition, Vol. 57, Issue 33
    • DOI: 10.1002/anie.201802745

    σ‐Noninnocence: Masked Phenyl‐Cation Transfer at Formal Ni IV
    journal, July 2019

    • Steen, Jelte S.; Knizia, Gerald; Klein, Johannes E. M. N.
    • Angewandte Chemie International Edition, Vol. 58, Issue 37
    • DOI: 10.1002/anie.201906658

    Homoleptic Trifluoromethyl Derivatives of Ag I and Ag III
    journal, August 2018

    • Joven-Sancho, Daniel; Baya, Miguel; Martín, Antonio
    • Chemistry - A European Journal, Vol. 24, Issue 50
    • DOI: 10.1002/chem.201802960

    Beyond Oxides: Nitride as a Ligand in a Neutral Ir IX NO 3 Molecule Bearing a Transition Metal at High Oxidation State
    journal, July 2019

    • Wolański, Łukasz; Domański, Mateusz; Grochala, Wojciech
    • Chemistry – A European Journal, Vol. 25, Issue 44
    • DOI: 10.1002/chem.201902142

    Unraveling the highest oxidation states of actinides in solid-state compounds with a particular focus on plutonium
    journal, January 2019

    • Ao, Bingyun; Lu, Haiyan; Yang, Zhenfei
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 9
    • DOI: 10.1039/c8cp05990j

    An Objective Alternative to IUPAC's Approach To Assign Oxidation States
    journal, August 2018

    • Postils, Verònica; Delgado‐Alonso, Carlos; Luis, Josep M.
    • Angewandte Chemie, Vol. 130, Issue 33
    • DOI: 10.1002/ange.201802745
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