Comparisons of lanthanide/actinide +2 ions in a tris(aryloxide)arene coordination environment

Megan E. Fieser; Chad T. Palumbo; Henry S. La Pierre; Dominik P. Halter; Vamsee K. Voora; Joseph W. Ziller; Filipp Furche; Karsten Meyer; William J. Evans

doi:10.1039/c7sc02337e

Comparisons of lanthanide/actinide +2 ions in a tris(aryloxide)arene coordination environment

Megan E. Fieser, Chad T. Palumbo, Henry S. La Pierre, Dominik P. Halter, Vamsee K. Voora, Joseph W. Ziller, Filipp Furche, Karsten Meyer, William J. Evans

Chemistry (Twin Cities)

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

57 Scopus citations

Abstract

A new series of Ln³⁺ and Ln²⁺ complexes has been synthesized using the tris(aryloxide)arene ligand system, ((^Ad,MeArO)₃mes)^3-, recently used to isolate a complex of U²⁺. The triphenol precursor, (^Ad,MeArOH)₃mes, reacts with the Ln³⁺ amides, Ln(NR₂)₃ (R = SiMe₃), to form a series of [((^Ad,MeArO)₃mes)Ln] complexes, 1-Ln. Crystallographic characterization was achieved for Ln = Nd, Gd, Dy, and Er. The complexes 1-Ln can be reduced with potassium graphite in the presence of 2.2.2-cryptand (crypt) to form highly absorbing solutions with properties consistent with Ln²⁺ complexes, [K(crypt)][((^Ad,MeArO)₃mes)Ln], 2-Ln. The synthesis of the Nd²⁺ complex [K(crypt)][((^Ad,MeArO)₃mes)Nd], 2-Nd, was unambiguously confirmed by X-ray crystallography. In the case of the other lanthanides, crystals were found to contain mixtures of 2-Ln co-crystallized with either a Ln³⁺ hydride complex, [K(crypt)][((^Ad,MeArO)₃mes)LnH], 3-Ln, for Ln = Gd, Dy, and Er, or a hydroxide complex, [K(crypt)][((^Ad,MeArO)₃mes)Ln(OH)], 4-Ln, for Ln = Dy. A Dy²⁺ complex with 18-crown-6 as the potassium chelator, [K(18-crown-6)(THF)₂][((^Ad,MeArO)₃mes)Dy], 5-Dy, was isolated as a co-crystallized mixture with the Dy³⁺ hydride complex, [K(18-crown-6)(THF)₂][((^Ad,MeArO)₃mes)DyH], 6-Dy. Structural comparisons of 1-Ln and 2-Ln are presented with respect to their uranium analogs and correlated with density functional theory calculations on their electronic structures.

Original language	English (US)
Pages (from-to)	7424-7433
Number of pages	10
Journal	Chemical Science
Volume	8
Issue number	11
DOIs	https://doi.org/10.1039/c7sc02337e
State	Published - 2017

Bibliographical note

Funding Information:
We thank the U.S. National Science Foundation for support of the experimental studies (CHE-1565776 to W. J. E.) and the theoretical studies (CHE-1464828 to F. F.). We also thank Professor Arnold L. Rheingold, Dr Milan Gembicky, Dr Jason R. Jones, and Dr Jordan F. Corbey for assistance with X-ray crystallography along with Professor A. S. Borovik and Victoria F. Oswald for spectroscopic assistance. We also thank the NSF for providing graduate fellowship support for C. T. P. (DGE-1321846). D. P. H acknowledges the Graduate School Molecular Science (GSMS) of FAU Erlangen-Nürnberg for generous support. The Bundesministerium für Bildung und Forschung (BMBF, support codes 02NUK012C and 02NUK020C), the FAU Erlangen-Nürnberg, and COST Action CM1006 are acknowledged for funding (to K. M.).

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© 2017 The Royal Society of Chemistry.

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10.1039/c7sc02337e

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@article{d1a3da4feed04778a4cf14a35acf5003,

title = "Comparisons of lanthanide/actinide +2 ions in a tris(aryloxide)arene coordination environment",

abstract = "A new series of Ln3+ and Ln2+ complexes has been synthesized using the tris(aryloxide)arene ligand system, ((Ad,MeArO)3mes)3-, recently used to isolate a complex of U2+. The triphenol precursor, (Ad,MeArOH)3mes, reacts with the Ln3+ amides, Ln(NR2)3 (R = SiMe3), to form a series of [((Ad,MeArO)3mes)Ln] complexes, 1-Ln. Crystallographic characterization was achieved for Ln = Nd, Gd, Dy, and Er. The complexes 1-Ln can be reduced with potassium graphite in the presence of 2.2.2-cryptand (crypt) to form highly absorbing solutions with properties consistent with Ln2+ complexes, [K(crypt)][((Ad,MeArO)3mes)Ln], 2-Ln. The synthesis of the Nd2+ complex [K(crypt)][((Ad,MeArO)3mes)Nd], 2-Nd, was unambiguously confirmed by X-ray crystallography. In the case of the other lanthanides, crystals were found to contain mixtures of 2-Ln co-crystallized with either a Ln3+ hydride complex, [K(crypt)][((Ad,MeArO)3mes)LnH], 3-Ln, for Ln = Gd, Dy, and Er, or a hydroxide complex, [K(crypt)][((Ad,MeArO)3mes)Ln(OH)], 4-Ln, for Ln = Dy. A Dy2+ complex with 18-crown-6 as the potassium chelator, [K(18-crown-6)(THF)2][((Ad,MeArO)3mes)Dy], 5-Dy, was isolated as a co-crystallized mixture with the Dy3+ hydride complex, [K(18-crown-6)(THF)2][((Ad,MeArO)3mes)DyH], 6-Dy. Structural comparisons of 1-Ln and 2-Ln are presented with respect to their uranium analogs and correlated with density functional theory calculations on their electronic structures.",

author = "Fieser, {Megan E.} and Palumbo, {Chad T.} and {La Pierre}, {Henry S.} and Halter, {Dominik P.} and Voora, {Vamsee K.} and Ziller, {Joseph W.} and Filipp Furche and Karsten Meyer and Evans, {William J.}",

note = "Funding Information: We thank the U.S. National Science Foundation for support of the experimental studies (CHE-1565776 to W. J. E.) and the theoretical studies (CHE-1464828 to F. F.). We also thank Professor Arnold L. Rheingold, Dr Milan Gembicky, Dr Jason R. Jones, and Dr Jordan F. Corbey for assistance with X-ray crystallography along with Professor A. S. Borovik and Victoria F. Oswald for spectroscopic assistance. We also thank the NSF for providing graduate fellowship support for C. T. P. (DGE-1321846). D. P. H acknowledges the Graduate School Molecular Science (GSMS) of FAU Erlangen-N{\"u}rnberg for generous support. The Bundesministerium f{\"u}r Bildung und Forschung (BMBF, support codes 02NUK012C and 02NUK020C), the FAU Erlangen-N{\"u}rnberg, and COST Action CM1006 are acknowledged for funding (to K. M.). Publisher Copyright: {\textcopyright} 2017 The Royal Society of Chemistry.",

year = "2017",

doi = "10.1039/c7sc02337e",

language = "English (US)",

volume = "8",

pages = "7424--7433",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "11",

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TY - JOUR

T1 - Comparisons of lanthanide/actinide +2 ions in a tris(aryloxide)arene coordination environment

AU - Fieser, Megan E.

AU - Palumbo, Chad T.

AU - La Pierre, Henry S.

AU - Halter, Dominik P.

AU - Voora, Vamsee K.

AU - Ziller, Joseph W.

AU - Furche, Filipp

AU - Meyer, Karsten

AU - Evans, William J.

N1 - Funding Information: We thank the U.S. National Science Foundation for support of the experimental studies (CHE-1565776 to W. J. E.) and the theoretical studies (CHE-1464828 to F. F.). We also thank Professor Arnold L. Rheingold, Dr Milan Gembicky, Dr Jason R. Jones, and Dr Jordan F. Corbey for assistance with X-ray crystallography along with Professor A. S. Borovik and Victoria F. Oswald for spectroscopic assistance. We also thank the NSF for providing graduate fellowship support for C. T. P. (DGE-1321846). D. P. H acknowledges the Graduate School Molecular Science (GSMS) of FAU Erlangen-Nürnberg for generous support. The Bundesministerium für Bildung und Forschung (BMBF, support codes 02NUK012C and 02NUK020C), the FAU Erlangen-Nürnberg, and COST Action CM1006 are acknowledged for funding (to K. M.). Publisher Copyright: © 2017 The Royal Society of Chemistry.

PY - 2017

Y1 - 2017

N2 - A new series of Ln3+ and Ln2+ complexes has been synthesized using the tris(aryloxide)arene ligand system, ((Ad,MeArO)3mes)3-, recently used to isolate a complex of U2+. The triphenol precursor, (Ad,MeArOH)3mes, reacts with the Ln3+ amides, Ln(NR2)3 (R = SiMe3), to form a series of [((Ad,MeArO)3mes)Ln] complexes, 1-Ln. Crystallographic characterization was achieved for Ln = Nd, Gd, Dy, and Er. The complexes 1-Ln can be reduced with potassium graphite in the presence of 2.2.2-cryptand (crypt) to form highly absorbing solutions with properties consistent with Ln2+ complexes, [K(crypt)][((Ad,MeArO)3mes)Ln], 2-Ln. The synthesis of the Nd2+ complex [K(crypt)][((Ad,MeArO)3mes)Nd], 2-Nd, was unambiguously confirmed by X-ray crystallography. In the case of the other lanthanides, crystals were found to contain mixtures of 2-Ln co-crystallized with either a Ln3+ hydride complex, [K(crypt)][((Ad,MeArO)3mes)LnH], 3-Ln, for Ln = Gd, Dy, and Er, or a hydroxide complex, [K(crypt)][((Ad,MeArO)3mes)Ln(OH)], 4-Ln, for Ln = Dy. A Dy2+ complex with 18-crown-6 as the potassium chelator, [K(18-crown-6)(THF)2][((Ad,MeArO)3mes)Dy], 5-Dy, was isolated as a co-crystallized mixture with the Dy3+ hydride complex, [K(18-crown-6)(THF)2][((Ad,MeArO)3mes)DyH], 6-Dy. Structural comparisons of 1-Ln and 2-Ln are presented with respect to their uranium analogs and correlated with density functional theory calculations on their electronic structures.

AB - A new series of Ln3+ and Ln2+ complexes has been synthesized using the tris(aryloxide)arene ligand system, ((Ad,MeArO)3mes)3-, recently used to isolate a complex of U2+. The triphenol precursor, (Ad,MeArOH)3mes, reacts with the Ln3+ amides, Ln(NR2)3 (R = SiMe3), to form a series of [((Ad,MeArO)3mes)Ln] complexes, 1-Ln. Crystallographic characterization was achieved for Ln = Nd, Gd, Dy, and Er. The complexes 1-Ln can be reduced with potassium graphite in the presence of 2.2.2-cryptand (crypt) to form highly absorbing solutions with properties consistent with Ln2+ complexes, [K(crypt)][((Ad,MeArO)3mes)Ln], 2-Ln. The synthesis of the Nd2+ complex [K(crypt)][((Ad,MeArO)3mes)Nd], 2-Nd, was unambiguously confirmed by X-ray crystallography. In the case of the other lanthanides, crystals were found to contain mixtures of 2-Ln co-crystallized with either a Ln3+ hydride complex, [K(crypt)][((Ad,MeArO)3mes)LnH], 3-Ln, for Ln = Gd, Dy, and Er, or a hydroxide complex, [K(crypt)][((Ad,MeArO)3mes)Ln(OH)], 4-Ln, for Ln = Dy. A Dy2+ complex with 18-crown-6 as the potassium chelator, [K(18-crown-6)(THF)2][((Ad,MeArO)3mes)Dy], 5-Dy, was isolated as a co-crystallized mixture with the Dy3+ hydride complex, [K(18-crown-6)(THF)2][((Ad,MeArO)3mes)DyH], 6-Dy. Structural comparisons of 1-Ln and 2-Ln are presented with respect to their uranium analogs and correlated with density functional theory calculations on their electronic structures.

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U2 - 10.1039/c7sc02337e

DO - 10.1039/c7sc02337e

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JO - Chemical Science

JF - Chemical Science

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Comparisons of lanthanide/actinide +2 ions in a tris(aryloxide)arene coordination environment

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