TY - JOUR
T1 - Metal versus Ligand Reduction in Ln3+ Complexes of a Mesitylene-Anchored Tris(Aryloxide) Ligand
AU - Palumbo, Chad T.
AU - Halter, Dominik P.
AU - Voora, Vamsee K.
AU - Chen, Guo P.
AU - Chan, Alan K.
AU - Fieser, Megan E.
AU - Ziller, Joseph W.
AU - Hieringer, Wolfgang
AU - Furche, Filipp
AU - Meyer, Karsten
AU - Evans, William J.
N1 - Publisher Copyright:
Copyright © 2018 American Chemical Society.
PY - 2018/3/5
Y1 - 2018/3/5
N2 - The synthesis of 4fn Ln3+ complexes of the tris(aryloxide) mesitylene ligand, ((Ad,MeArO)3mes)3-, 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(SiMe3)2)3] (Ln = La, Ce, Pr, Sm, Yb) with the tris(phenol) (Ad,MeArOH)3mes yielded the Ln3+ complexes [((Ad,MeArO)3mes)Ln] (Ln = La, Ce, Pr, Sm, Yb), 1-Ln. Single electron reduction of each 4fn complex, 1-Ln, using potassium yielded the reduced products, [K(2.2.2-cryptand)][((Ad,MeArO)3mes)Ln] (Ln = La, Ce, Pr, Sm, Yb), 2-Ln. The Sm and Yb complexes have properties consistent with the presence of Ln2+ ions with traditional 4fn+1 electron configurations. However, the La, Ce, and Pr complexes appear to formally contain Ln3+ ions and ((Ad,MeArO)3mes)4- ligands. Structural comparisons of the [((Ad,MeArO)3mes)Ln] and [((Ad,MeOAr)3mes)Ln]1- complexes along with UV-vis absorption and EPR spectroscopy as well as density functional theory calculations support these ground state assignments.
AB - The synthesis of 4fn Ln3+ complexes of the tris(aryloxide) mesitylene ligand, ((Ad,MeArO)3mes)3-, 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(SiMe3)2)3] (Ln = La, Ce, Pr, Sm, Yb) with the tris(phenol) (Ad,MeArOH)3mes yielded the Ln3+ complexes [((Ad,MeArO)3mes)Ln] (Ln = La, Ce, Pr, Sm, Yb), 1-Ln. Single electron reduction of each 4fn complex, 1-Ln, using potassium yielded the reduced products, [K(2.2.2-cryptand)][((Ad,MeArO)3mes)Ln] (Ln = La, Ce, Pr, Sm, Yb), 2-Ln. The Sm and Yb complexes have properties consistent with the presence of Ln2+ ions with traditional 4fn+1 electron configurations. However, the La, Ce, and Pr complexes appear to formally contain Ln3+ ions and ((Ad,MeArO)3mes)4- ligands. Structural comparisons of the [((Ad,MeArO)3mes)Ln] and [((Ad,MeOAr)3mes)Ln]1- complexes along with UV-vis absorption and EPR spectroscopy as well as density functional theory calculations support these ground state assignments.
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U2 - 10.1021/acs.inorgchem.7b03236
DO - 10.1021/acs.inorgchem.7b03236
M3 - Article
C2 - 29457716
AN - SCOPUS:85042353767
SN - 0020-1669
VL - 57
SP - 2823
EP - 2833
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 5
ER -