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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 = {Mon Feb 19 00:00:00 EST 2018},
month = {Mon Feb 19 00:00:00 EST 2018}
}
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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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