Volume 57, Issue 12
Communication

On the Upper Limits of Oxidation States in Chemistry

Dr. Shu‐Xian Hu

Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Department of Chemistry, Tsinghua University, Beijing, 100084 China

Beijing Computer Science Research Center, Haidian, Beijing, 100193 China

These authors contributed equally to this work.

Search for more papers by this author
M. Sc. Wan‐Lu Li

Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Department of Chemistry, Tsinghua University, Beijing, 100084 China

These authors contributed equally to this work.

Search for more papers by this author
M. Sc. Jun‐Bo Lu

Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Department of Chemistry, Tsinghua University, Beijing, 100084 China

Search for more papers by this author
Dr. Junwei Lucas Bao

Chemical Theory Center, Department of Chemistry, and Minnesota Supercomputing Institute, University of Minnesota, Minneapolis, MN, 55455-0431 USA

Search for more papers by this author
Dr. Haoyu S. Yu

Chemical Theory Center, Department of Chemistry, and Minnesota Supercomputing Institute, University of Minnesota, Minneapolis, MN, 55455-0431 USA

Search for more papers by this author
Prof. Dr. Donald G. Truhlar

Chemical Theory Center, Department of Chemistry, and Minnesota Supercomputing Institute, University of Minnesota, Minneapolis, MN, 55455-0431 USA

Search for more papers by this author
Dr. John K. Gibson

Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720 USA

Search for more papers by this author
Dr. Joaquim Marçalo

Centro de Ciências e Tecnologias Nucleares, Instituto Superior Técnico, Universidade de Lisboa, 2695-066 Bobadela LRS, Portugal

Search for more papers by this author
Prof. Dr. Mingfei Zhou

Department of Chemistry, Fudan University, Shanghai, 200433 China

Search for more papers by this author
Prof. Dr. Sebastian Riedel

Anorganische Chemie, Institut für Chemie und Biochemie, Freie Universität Berlin, 14195 Berlin, Germany

Search for more papers by this author
Prof. Dr. W. H. Eugen Schwarz

Corresponding Author

E-mail address: eugen.schwarz@uni-siegen.de

Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Department of Chemistry, Tsinghua University, Beijing, 100084 China

Physical and Theoretical Chemistry Lab, Universität Siegen, 57068 Siegen, Germany

Search for more papers by this author
Prof. Dr. Jun Li

Corresponding Author

E-mail address: junli@tsinghua.edu.cn

Key Laboratory of Organic Optoelectronics & Molecular Engineering of the Ministry of Education, Department of Chemistry, Tsinghua University, Beijing, 100084 China

Search for more papers by this author
First published: 04 January 2018
Citations: 24

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.

Number of times cited according to CrossRef: 24

  • The duality of electron localization and covalency in lanthanide and actinide metallocenes, Chemical Science, 10.1039/C9SC06114B, (2020).
  • Exploring the Limits of Transition‐Metal Fluorination at High Pressures, Angewandte Chemie International Edition, 10.1002/anie.202002339, 59, 23, (9155-9162), (2020).
  • Exploring the Limits of Transition‐Metal Fluorination at High Pressures, Angewandte Chemie, 10.1002/ange.202002339, 132, 23, (9240-9247), (2020).
  • Evaluation of chemical bonding and electronic structures in trisodium actinate for actinide series from thorium to curium, Computational Materials Science, 10.1016/j.commatsci.2020.109770, 182, (109770), (2020).
  • A Cornucopia of Iridium Nitrogen Compounds Produced from Laser‐Ablated Iridium Atoms and Dinitrogen, Chemistry – A European Journal, 10.1002/chem.201905514, 26, 33, (7384-7394), (2020).
  • CO Oxidation Catalyzed by the Neutral Cluster IrAl2O8 with Iridium in A High Oxidation State of VI, The Journal of Physical Chemistry C, 10.1021/acs.jpcc.0c01562, (2020).
  • Single Atom AuI-N3 Site for Acetylene Hydrochlorination Reaction, ACS Catalysis, 10.1021/acscatal.9b05212, (2020).
  • Physical origin of chemical periodicities in the system of elements, Pure and Applied Chemistry, 10.1515/pac-2019-0901, 0, 0, (2019).
  • Chemical evidence of the stability of praseodymium( v ) in gas-phase oxide nitrate complexes , Chemical Communications, 10.1039/C9CC08006F, (2019).
  • Unexpected Molecular Structure of a Putative Rhenium‐Dioxo‐Benzocarbaporphyrin Complex. Implications for the Highest Transition Metal Valence in a Porphyrin‐Type Ligand Environment, ChemistryOpen, 10.1002/open.201900271, 8, 10, (1298-1302), (2019).
  • Beyond Oxides: Nitride as a Ligand in a Neutral IrIXNO3 Molecule Bearing a Transition Metal at High Oxidation State, Chemistry – A European Journal, 10.1002/chem.201902142, 25, 44, (10290-10293), (2019).
  • σ‐Noninnocence: Masked Phenyl‐Cation Transfer at Formal NiIV, Angewandte Chemie International Edition, 10.1002/anie.201906658, 58, 37, (13133-13139), (2019).
  • σ‐Noninnocence: Masked Phenyl‐Cation Transfer at Formal NiIV, Angewandte Chemie, 10.1002/ange.201906658, 131, 37, (13267-13273), (2019).
  • Exploring the electronic structure and stability of HgF6: Exact 2-Component (X2C) relativistic DFT and NEVPT2 studies, Computational and Theoretical Chemistry, 10.1016/j.comptc.2019.05.007, 1160, (14-18), (2019).
  • Theoretical Search for the Highest Valence States of the Coinage Metals: Roentgenium Heptafluoride May Exist, Inorganic Chemistry, 10.1021/acs.inorgchem.9b01139, (2019).
  • Unconventional Look at the Diameters of Quantum Systems: Could the Characteristic Atomic Radius Be Interpreted as a Reactivity Measure?, The Journal of Physical Chemistry C, 10.1021/acs.jpcc.9b00221, (2019).
  • Relativity–Induced Bonding Pattern Change in Coinage Metal Dimers M 2 (M = Cu, Ag, Au, Rg) , Inorganic Chemistry, 10.1021/acs.inorgchem.8b00438, 57, 9, (5499-5506), (2018).
  • Homoleptic Trifluoromethyl Derivatives of AgI and AgIII , Chemistry – A European Journal, 10.1002/chem.201802960, 24, 50, (13098-13101), (2018).
  • An Objective Alternative to IUPAC's Approach To Assign Oxidation States, Angewandte Chemie International Edition, 10.1002/anie.201802745, 57, 33, (10525-10529), (2018).
  • An Objective Alternative to IUPAC's Approach To Assign Oxidation States, Angewandte Chemie, 10.1002/ange.201802745, 130, 33, (10685-10689), (2018).
  • Unraveling the highest oxidation states of actinides in solid-state compounds with a particular focus on plutonium, Physical Chemistry Chemical Physics, 10.1039/C8CP05990J, (2018).
  • Pentavalent Curium, Berkelium, and Californium in Nitrate Complexes: Extending Actinide Chemistry and Oxidation States, Inorganic Chemistry, 10.1021/acs.inorgchem.8b01450, 57, 15, (9453-9467), (2018).
  • Chemical Bonding of Crystalline LnB 6 (Ln = La–Lu) and Its Relationship with Ln 2 B 8 Gas-Phase Complexes , Inorganic Chemistry, 10.1021/acs.inorgchem.8b02263, (2018).
  • Lanthanides with Unusually Low Oxidation States in the PrB 3 – and PrB 4 – Boride Clusters , Inorganic Chemistry, 10.1021/acs.inorgchem.8b02572, (2018).

The full text of this article hosted at iucr.org is unavailable due to technical difficulties.