Accessing the +IV Oxidation State in Molecular Complexes of Praseodymium
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,...
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| Veröffentlicht in: | Journal of the American Chemical Society 2020-03, Vol.142 (12), p.5538-5542 |
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| Hauptverfasser: | , , , , , , |
| Format: | Artikel |
| Sprache: | eng |
| Online-Zugang: | Volltext |
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| Zusammenfassung: | 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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| ISSN: | 0002-7863 1520-5126 |
| DOI: | 10.1021/jacs.0c01204 |