Accessing the +IV Oxidation State in Molecular Complexes of Praseodymium

Cite this: J. Am. Chem. Soc. 2020, 142, 12, 5538–5542
Publication Date (Web):March 5, 2020
https://doi.org/10.1021/jacs.0c01204
Copyright © 2020 American Chemical Society
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Abstract

Out of the 14 lanthanide (Ln) ions, molecular complexes of Ln(IV) were known only for cerium and more recently terbium. Here we demonstrate that the +IV oxidation state is also accessible for the large praseodymium (Pr) cation. The oxidation of the tetrakis(triphenysiloxide) Pr(III) ate complex, [KPr(OSiPh3)4(THF)3], 1-PrPh, with [N(C6H4Br)3][SbCl6], affords the Pr(IV) complex [Pr(OSiPh3)4(MeCN)2], 2-PrPh, which is stable once isolated. The solid state structure, UV–visible spectroscopy, magnetometry, and cyclic voltammetry data along with the DFT computations of the 2-PrPh complex unambiguously confirm the presence of Pr(IV).

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.0c01204.

  • Additional spectroscopic, electrochemical characterization, magnetism, and structural details for 1-PrOtBu, 1-LnPh (Ln = Ce, Pr), 2-PrPh, and 3 (PDF)

  • Crystallographic data for 2-PrPh (CIF)

  • Crystallographic data for 3 (CIF)

  • Crystallographic data for 1-PrPh (CIF)

  • Crystallographic data for 1-PrOtBu (CIF)

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