On the Upper Limits of Oxidation States in Chemistry |
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| Authors: | Dr Shu‐Xian Hu M Sc Wan‐Lu Li M Sc Jun‐Bo Lu Dr Junwei Lucas Bao Dr Haoyu S Yu Prof Dr Donald G Truhlar Dr John K Gibson Dr Joaquim Marçalo Prof Dr Mingfei Zhou Prof Dr Sebastian Riedel Prof Dr W H Eugen Schwarz Prof Dr Jun Li |
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| Institution: | 1. Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Department of Chemistry, Tsinghua University, Beijing, China;2. Beijing Computer Science Research Center, Beijing, China;3. Chemical Theory Center, Department of Chemistry, and Minnesota Supercomputing Institute, University of Minnesota, Minneapolis, MN, USA;4. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA;5. Centro de Ciências e Tecnologias Nucleares, Instituto Superior Técnico, Universidade de Lisboa, Bobadela LRS, Portugal;6. Department of Chemistry, Fudan University, Shanghai, China;7. Anorganische Chemie, Institut für Chemie und Biochemie, Freie Universit?t Berlin, Berlin, Germany;8. Physical and Theoretical Chemistry Lab, Universit?t Siegen, Siegen, Germany |
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| 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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| Keywords: | bonding theory computational chemistry oxidation states oxides transition metals |
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