Accessing the +IV Oxidation State in Molecular Complexes of Praseodymium - PubMed (original) (raw)
. 2020 Mar 25;142(12):5538-5542.
doi: 10.1021/jacs.0c01204. Epub 2020 Mar 11.
Affiliations
- PMID: 32134644
- DOI: 10.1021/jacs.0c01204
Accessing the +IV Oxidation State in Molecular Complexes of Praseodymium
Aurélien R Willauer et al. J Am Chem Soc. 2020.
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-Pr Ph, with [N(C6H4Br)3][SbCl6], affords the Pr(IV) complex [Pr(OSiPh3)4(MeCN)2], 2-Pr Ph, 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-Pr Ph complex unambiguously confirm the presence of Pr(IV).
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