On the Upper Limits of Oxidation States in Chemistry

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

doi:10.1002/anie.201711450

Title: On the Upper Limits of Oxidation States in Chemistry

Journal Article · 19 February 2018 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.201711450 · OSTI ID:1461134

Hu, Shu-Xian ^[1]; Li, Wan-Lu ^[2]; Lu, Jun-Bo ^[3]; Bao, Junwei Lucas ^[4]; Yu, Haoyu S. ^[4];

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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)
Tsinghua Univ., Beijing (China). Key Lab. of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Dept. of Chemistry
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
Univ. of Minnesota, Minneapolis, MN (United States). Minnesota Supercomputing Inst., Chemical Theory Center, Dept. of Chemistry
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Univ. de Lisboa, Bobadela (Portugal). Centro de Ciencias e Tecnologias Nucleares, Inst. Superior Tecnico
Fudan Univ., Shanghai (China). Dept. of Chemistry
Freie Univ. Berlin, Berlin (Germany). Anorganische Chemie, Inst. fur Chemie und Biochemie
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.

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.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); USDOE

Grant/Contract Number:: AC02-05CH11231; 21590792; 91426302; 91645203; 2170106; 21433005; U1530401; SC0015997; UID/Multi/04349/2013; AC02-05CH1123

OSTI ID:: 1461134

Alternate ID(s):: OSTI ID: 1422008

Journal Information:: Angewandte Chemie (International Edition), Vol. 57, Issue 12; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 42 works

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