Lanthanides with Unusually Low Oxidation States in the PrB3- and PrB4- Boride Clusters

doi:10.1021/acs.inorgchem.8b02572

. 2019 Jan 7;58(1):411-418.

doi: 10.1021/acs.inorgchem.8b02572. Epub 2018 Dec 13.

Lanthanides with Unusually Low Oxidation States in the PrB₃^- and PrB₄^- Boride Clusters

Xin Chen¹, Teng-Teng Chen², Wan-Lu Li¹, Jun-Bo Lu¹, Li-Juan Zhao¹, Tian Jian², Han-Shi Hu¹, Lai-Sheng Wang², Jun Li^{1

3}

Affiliations

¹ Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education , Tsinghua University , Beijing 100084 , China.
² Department of Chemistry , Brown University , Providence , Rhode Island 02912 , United States.
³ Department of Chemistry , Southern University of Science and Technology , Shenzhen , Guangdong 518055 , China.

PMID: 30543295
DOI: 10.1021/acs.inorgchem.8b02572

Lanthanides with Unusually Low Oxidation States in the PrB₃^- and PrB₄^- Boride Clusters

Xin Chen et al. Inorg Chem. 2019.

. 2019 Jan 7;58(1):411-418.

doi: 10.1021/acs.inorgchem.8b02572. Epub 2018 Dec 13.

Authors

Xin Chen¹, Teng-Teng Chen², Wan-Lu Li¹, Jun-Bo Lu¹, Li-Juan Zhao¹, Tian Jian², Han-Shi Hu¹, Lai-Sheng Wang², Jun Li^{1

3}

Affiliations

¹ Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education , Tsinghua University , Beijing 100084 , China.
² Department of Chemistry , Brown University , Providence , Rhode Island 02912 , United States.
³ Department of Chemistry , Southern University of Science and Technology , Shenzhen , Guangdong 518055 , China.

PMID: 30543295
DOI: 10.1021/acs.inorgchem.8b02572

Abstract

Lanthanide elements typically exhibit a +III oxidation state (OS) in chemical compounds with a few in +IV or even +V OS. Although lanthanides with +II OS have been observed recently in organometallic compounds, +I OS is extremely rare. Using a joint photoelectron spectroscopy and quantum theoretical study, we have found two low OS lanthanides in doped boron clusters, PrB₃^- and PrB₄^-. These two clusters are shown to have planar structures, in which the Pr atom is bonded to the aromatic boron clusters via two Pr-B σ bonds. Chemical bonding and electronic structure analyses reveal that the Pr atom is in a very low OS in the two boride clusters: +II in PrB₃^- and +I in PrB₄^-. The current finding suggests that there should exist a whole class of boride complexes featuring rather low-valent lanthanides and expands the frontier of lanthanide chemistry.

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Lanthanides with Unusually Low Oxidation States in the PrB₃^- and PrB₄^- Boride Clusters

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Lanthanides with Unusually Low Oxidation States in the PrB₃^- and PrB₄^- Boride Clusters

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Abstract

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