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 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 Pr(V) oxidation state, thus demonstrating that the pentavalent state is viable for lanthanide elements in a suitable coordination environment.
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.
Qingnan
Q
Zhang
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing, 100084, China.
Shu-Xian
SX
Hu
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.
Hui
H
Qu
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing, 100084, China.
Jing
J
Su
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.
Guanjun
G
Wang
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing, 100084, China.
Jun-Bo
JB
Lu
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.
Mohua
M
Chen
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. mfzhou@fudan.edu.cn.
Mingfei
M
Zhou
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing, 100084, China. junli@tsinghua.edu.cn.
Jun
J
Li
infrared photodissociation spectroscopy; lanthanides; matrix isolation; oxidation state; praseodymium