Rare-Earth Metal(II) Aryloxides

Structure, Synthesis, and EPR Spectroscopy of [K(2.2.2-cryptand)][Sc(OC6H2tBu2-2,6-Me-4)3]

Samuel A. Moehring, María J. Beltrán-Leiva, Dayán Páez-Hernández, Ramiro Arratia-Pérez, Joseph W. Ziller, William J. Evans

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)18059-18067
Number of pages9
JournalChemistry - A European Journal
Volume24
Issue number68
DOIs
Publication statusPublished - 5 Dec 2018

Fingerprint

Rare Earth Metals
Rare earths
Paramagnetic resonance
Spectroscopy
Metals
Ligands
Graphite
X ray crystallography
Structural analysis
Density functional theory
Potassium
Crystal structure
Ions
Oxygen
X rays
Atoms
Oxidation
Temperature
cryptand

Keywords

  • aryloxides
  • low-valent metals
  • rare-earth metals
  • reduction
  • scandium

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

Cite this

Moehring, Samuel A. ; Beltrán-Leiva, María J. ; Páez-Hernández, Dayán ; Arratia-Pérez, Ramiro ; Ziller, Joseph W. ; Evans, William J. / Rare-Earth Metal(II) Aryloxides : Structure, Synthesis, and EPR Spectroscopy of [K(2.2.2-cryptand)][Sc(OC6H2tBu2-2,6-Me-4)3]. In: Chemistry - A European Journal. 2018 ; Vol. 24, No. 68. pp. 18059-18067.
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abstract = "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.",
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Rare-Earth Metal(II) Aryloxides : Structure, Synthesis, and EPR Spectroscopy of [K(2.2.2-cryptand)][Sc(OC6H2tBu2-2,6-Me-4)3]. / Moehring, Samuel A.; Beltrán-Leiva, María J.; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro; Ziller, Joseph W.; Evans, William J.

In: Chemistry - A European Journal, Vol. 24, No. 68, 05.12.2018, p. 18059-18067.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Rare-Earth Metal(II) Aryloxides

T2 - Structure, Synthesis, and EPR Spectroscopy of [K(2.2.2-cryptand)][Sc(OC6H2tBu2-2,6-Me-4)3]

AU - Moehring, Samuel A.

AU - Beltrán-Leiva, María J.

AU - Páez-Hernández, Dayán

AU - Arratia-Pérez, Ramiro

AU - Ziller, Joseph W.

AU - Evans, William J.

PY - 2018/12/5

Y1 - 2018/12/5

N2 - 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.

AB - 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.

KW - aryloxides

KW - low-valent metals

KW - rare-earth metals

KW - reduction

KW - scandium

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