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Metal versus Ligand Reduction in Ln 3+ Complexes of a Mesitylene-Anchored Tris(Aryloxide) Ligand.
- Source :
-
Inorganic chemistry [Inorg Chem] 2018 Mar 05; Vol. 57 (5), pp. 2823-2833. Date of Electronic Publication: 2018 Feb 19. - Publication Year :
- 2018
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Abstract
- The synthesis of 4f <superscript>n</superscript> Ln <superscript>3+</superscript> complexes of the tris(aryloxide) mesitylene ligand, (( <superscript>Ad,Me</superscript> ArO) <subscript>3</subscript> mes) <superscript>3-</superscript> , with Ln = La, Ce, Pr, Sm, and Yb, and their reduction with potassium have revealed that this ligand system can be redox active with some metals. Protonolysis of [Ln(N(SiMe <subscript>3</subscript> ) <subscript>2</subscript> ) <subscript>3</subscript> ] (Ln = La, Ce, Pr, Sm, Yb) with the tris(phenol) ( <superscript>Ad,Me</superscript> ArOH) <subscript>3</subscript> mes yielded the Ln <superscript>3+</superscript> complexes [(( <superscript>Ad,Me</superscript> ArO) <subscript>3</subscript> mes)Ln] (Ln = La, Ce, Pr, Sm, Yb), 1-Ln. Single electron reduction of each 4f <superscript>n</superscript> complex, 1-Ln, using potassium yielded the reduced products, [K(2.2.2-cryptand)][(( <superscript>Ad,Me</superscript> ArO) <subscript>3</subscript> mes)Ln] (Ln = La, Ce, Pr, Sm, Yb), 2-Ln. The Sm and Yb complexes have properties consistent with the presence of Ln <superscript>2+</superscript> ions with traditional 4f <superscript>n+1</superscript> electron configurations. However, the La, Ce, and Pr complexes appear to formally contain Ln <superscript>3+</superscript> ions and (( <superscript>Ad,Me</superscript> ArO) <subscript>3</subscript> mes) <superscript>4-</superscript> ligands. Structural comparisons of the [(( <superscript>Ad,Me</superscript> ArO) <subscript>3</subscript> mes)Ln] and [(( <superscript>Ad,Me</superscript> OAr) <subscript>3</subscript> mes)Ln] <superscript>1-</superscript> complexes along with UV-vis absorption and EPR spectroscopy as well as density functional theory calculations support these ground state assignments.
Details
- Language :
- English
- ISSN :
- 1520-510X
- Volume :
- 57
- Issue :
- 5
- Database :
- MEDLINE
- Journal :
- Inorganic chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 29457716
- Full Text :
- https://doi.org/10.1021/acs.inorgchem.7b03236