Rare-Earth Metal(II) Aryloxides: Structure, Synthesis, and EPR Spectroscopy of [K(2.2.2-cryptand)][Sc(OC6H2tBu2-2,6-Me-4)3]
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Fecha
2018-12
Profesor/a Guía
Facultad/escuela
Idioma
en
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Título del volumen
Editor
Wiley-VCH Verlag
Nombre de Curso
Licencia CC
Licencia CC
Resumen
The suitability of aryloxide ligands for stabilizing +2 oxidation states of Sc and Y has been examined and EPR evidence indicating the first O-donor complexes of ScII and YII has been obtained, as well as an X-ray crystal structure of a ScII aryloxide complex. The trivalent rare-earth metal aryloxide precursors, Ln(OAr′)3, 1-Ln (Ln=Sc, Y, Gd, Dy, Ho, Er; OAr′=OC6H2tBu2-2,6-Me-4), were synthesized from the corresponding rare-earth metal trichlorides and LiOAr′⋅OEt2. Reduction of THF solutions of 1-Ln with potassium graphite in the presence of 2.2.2-cryptand (crypt) yielded dark-colored solutions, 2-Ln, whose EPR spectra at 77 K are characteristic of the LnII ions: a two-line spectrum (g∥=1.99, g□=1.97, Aave=154 G) for 2-Y and an eight-line spectrum (gave=2.01 and Aave=291 G) for 2-Sc. Solutions of 2-Y decompose within one minute at room temperature, wheras 2-Sc persists up to 40 min at room temperature. 2-Sc was identified by X-ray crystallography as [K(crypt)][Sc(OAr′)3], which has a trigonal-planar arrangement of oxygen-donor atoms around ScII. Analogous reductions of 1-Ln for Ln=Gd, Dy, Ho, and Er also gave dark solutions of limited stability. Theoretical analysis using time-dependent density functional theory (TD-DFT) along with complete active space self-consistent field (CASSCF) methods, and structural analysis with the Guzei ligand solid angle G-parameter method are presented. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Indexación Scopus
Palabras clave
Crystal structure, Density functional theory, Electron spin resonance spectroscopy, Hydrogen bonds, Large scale systems, Ligands, Rare earth elements, Reduction, Scandium, Spectrum analysis, Uranium mines, X ray crystallography
Citación
Chemistry - A European Journal Volume 24, Issue 68, Pages 18059 - 180675 December 2018
DOI
10.1002/chem.201803807