Pentavalent Lanthanide Compounds: Formation and Characterization of Praseodymium(V) Oxides

The chemistry of lanthanides (Ln=La–Lu) is dominated by the low‐valent +3 or +2 oxidation state because of the chemical inertness of the valence 4f electrons. The highest known oxidation state of the whole lanthanide series is +4 for Ce, Pr, Nd, Tb, and Dy. We report the formation of the lanthanide...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2016-06, Vol.55 (24), p.6896-6900
Main Authors: Zhang, Qingnan, Hu, Shu-Xian, Qu, Hui, Su, Jing, Wang, Guanjun, Lu, Jun-Bo, Chen, Mohua, Zhou, Mingfei, Li, Jun
Format: Article
Language:English
Subjects:
infrared photodissociation spectroscopy
lanthanides
matrix isolation
Oxidation
oxidation state
praseodymium
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Summary:The chemistry of lanthanides (Ln=La–Lu) is dominated by the low‐valent +3 or +2 oxidation state because of the chemical inertness of the valence 4f electrons. The highest known oxidation state of the whole lanthanide series is +4 for Ce, Pr, Nd, Tb, and Dy. We report the formation of the lanthanide oxide species PrO4 and PrO2+ complexes in the gas phase and in a solid noble‐gas matrix. Combined infrared spectroscopic and advanced quantum chemistry studies show that these species have the unprecedented PrV oxidation state, thus demonstrating that the pentavalent state is viable for lanthanide elements in a suitable coordination environment. Very im‐Pr‐essive: Infrared spectroscopic studies and quantum chemical calculations show that PrO4 and PrO2+ oxide species involve the unprecedented PrV oxidation state. In the gas phase, species such as [(PrO)+(O2)n] and [(PrO2)+(O2)n] (n=1–7), which contain the linear PrO2+ ion, are formed. These studies demonstrate that the pentavalent state is viable for lanthanide elements in a suitable coordination environment.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201602196