Metal versus Ligand Reduction in Ln3+ Complexes of a Mesitylene-Anchored Tris(Aryloxide) Ligand

Chad T. Palumbo; Dominik P. Halter; Vamsee K. Voora; Guo P. Chen; Alan K. Chan; Megan E. Fieser; Joseph W. Ziller; Wolfgang Hieringer; Filipp Furche; Karsten Meyer; William J. Evans

doi:10.1021/acs.inorgchem.7b03236

Metal versus Ligand Reduction in Ln³⁺ Complexes of a Mesitylene-Anchored Tris(Aryloxide) Ligand

Chad T. Palumbo
, Dominik P. Halter
, Vamsee K. Voora
, Guo P. Chen
, Alan K. Chan
, Megan E. Fieser
, Joseph W. Ziller
, Wolfgang Hieringer
, Filipp Furche
, Karsten Meyer
, William J. Evans

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

54 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	2823-2833
Number of pages	11
Journal	Inorganic chemistry
Volume	57
Issue number	5
DOIs	https://doi.org/10.1021/acs.inorgchem.7b03236
State	Published - Mar 5 2018

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Publisher Copyright:
Copyright © 2018 American Chemical Society.

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10.1021/acs.inorgchem.7b03236

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@article{fca45b9d5882401bb816f52af9a5832a,

title = "Metal versus Ligand Reduction in Ln3+ Complexes of a Mesitylene-Anchored Tris(Aryloxide) Ligand",

abstract = "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.",

author = "Palumbo, \{Chad T.\} and Halter, \{Dominik P.\} and Voora, \{Vamsee K.\} and Chen, \{Guo P.\} and Chan, \{Alan K.\} and Fieser, \{Megan E.\} and Ziller, \{Joseph W.\} and Wolfgang Hieringer and Filipp Furche and Karsten Meyer and Evans, \{William J.\}",

note = "Publisher Copyright: Copyright {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = mar,

day = "5",

doi = "10.1021/acs.inorgchem.7b03236",

language = "English (US)",

volume = "57",

pages = "2823--2833",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "5",

}

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.

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.

UR - https://www.scopus.com/pages/publications/85042353767

UR - https://www.scopus.com/pages/publications/85042353767#tab=citedBy

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 -