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On the oxidation states of metal elements in MO3 - (M=V, Nb, Ta, Db, Pr, Gd, Pa) anions

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Abstract

Relativistic quantum chemistry investigations are carried out to tackle the puzzling oxidation state problem in a series of MO -3 trioxide anions of all d- and f-block elements with five valence electrons. We have shown here that while the oxidation states of V, Nb, Ta, Db, Pa are, as usual, all +V with divalent oxygen O(-II) in MO -3 anions, the lanthanide elements Pr and Gd cannot adopt such high +V oxidation state in similar trioxide anions. Instead, lanthanide element Gd retains its usual +III oxidation state, while Pr retains a +IV oxidation state, thus forcing oxygen into a non-innocent ligand with an uncommon monovalent radical (O•) of oxidation state -I. A unique Pr• - •(O)3 biradical with highly delocalized unpairing electron density on Pr(IV) and three O atoms is found to be responsible for stabilizing the monovalent-oxygen species in PrO -3 ion, while GdO -3 ion is in fact an OGd+(O 2-2 ) complex with Gd(III). These results show that a naïve assignment of oxidation state of a chemical element without electronic structure analysis can lead to erroneous conclusions.

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Authors and Affiliations

  1. Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education; Department of Chemistry, Tsinghua University, Beijing, 100084, China

    Jing Su, Shuxian Hu, Wei Huang & Jun Li

  2. Collaborative Innovation Center of Chemistry for Energy Materials, Department of Chemistry; Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai, 200433, China

    Mingfei Zhou

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  1. Jing Su
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  2. Shuxian Hu
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  3. Wei Huang
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  4. Mingfei Zhou
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  5. Jun Li
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Correspondence to Mingfei Zhou or Jun Li.

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Su, J., Hu, S., Huang, W. et al. On the oxidation states of metal elements in MO3 - (M=V, Nb, Ta, Db, Pr, Gd, Pa) anions. Sci. China Chem. 59, 442–451 (2016). https://doi.org/10.1007/s11426-015-5481-z

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  • DOI: https://doi.org/10.1007/s11426-015-5481-z

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