Employing Lewis Acidity to Generate Bimetallic Lanthanide Complexes

Bonnie E. Klamm; Thomas E. Albrecht-Schmitt; Ryan E. Baumbach; Brennan S. Billow; Frankie D. White; Stosh A. Kozimor; Brian L. Scott; Aaron M. Tondreau

doi:10.1021/acs.inorgchem.0c00775

Employing Lewis Acidity to Generate Bimetallic Lanthanide Complexes

Bonnie E. Klamm, Thomas E. Albrecht-Schmitt, Ryan E. Baumbach, Brennan S. Billow, Frankie D. White, Stosh A. Kozimor, Brian L. Scott, Aaron M. Tondreau

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

4 Scopus citations

Abstract

With the advent of lanthanide-based technologies, there is a clear need to advance the fundamental understanding of 4f-element chelation chemistry. Herein, we contribute to a growing body of lanthanide chelation chemistry and report the synthesis of bimetallic 4f-element complexes within an imine/hemiacetalate framework, Ln2TPTOMe [Ln = lanthanide; TPTOMe = tris(pyridineimine)(Tren)tris(methoxyhemiacetalate); Tren = tris(2-aminoethylamine)]. These products are generated from hydrolysis and methanolysis of the cage ligand tris(pyridinediimine)bis(Tren) (TPT; Tadanobu et al. Chem. Lett. 1993, 22 (5), 859-862) likely facilitated by inductive effects stemming from the Lewis acidic lanthanide cations. These complexes are interesting because they result from imine cleavage to generate two metal binding sites: one pocketed site within the macrocycle and the other terminal site capping a hemiacetalate moiety. A clear demarcation in reactivity is observed between samarium and europium, where the lighter and larger lanthanides generate a mixture of products, Ln2TPTOMe and LnTPT. Meanwhile, the heavier and smaller lanthanides generate exclusively bimetallic Ln2TPTOMe. The cleavage reactivity to form Ln2TPTOMe was extended beyond methanol to include other primary alcohols.

Original language	English
Pages (from-to)	8642-8646
Number of pages	5
Journal	Inorganic Chemistry
Volume	59
Issue number	13
DOIs	https://doi.org/10.1021/acs.inorgchem.0c00775
State	Published - Jul 6 2020
Externally published	Yes

Funding

This work was conceived and executed at LANL. Funding at LANL was provided by the Director, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, Heavy Element Chemistry Program of the U.S. Department of Energy (DOE), the Laboratory Directed Research and Development program of LANL under Projects 20180128ER and 2019057ECR, the Seaborg Institute, and a Summer Research Fellowship awarded to B.E.K. B.E.K. and T.E.A.-S. thank the Chemical Sciences, Geosciences, and Biosciences Division of the Office of Basic Energy Sciences of the U.S. DOE for supporting the research as part of the Center for Actinide Science and Technology funded by the U.S. DOE, Office of Science, Office of Basic Energy Sciences, under Award DE-SC0016568. A portion of this work was performed at the National High Magnetic Field Laboratory, which is supported by National Science Foundation Cooperative Agreement DMR-1644779 and the State of Florida.

Funders	Funder number
Seaborg Institute
State of Florida
National Science Foundation	DMR-1644779
U.S. Department of Energy	DE-SC0016568
Office of Science
Basic Energy Sciences
Laboratory Directed Research and Development
Los Alamos National Laboratory	20180128ER, 2019057ECR
Chemical Sciences, Geosciences, and Biosciences Division

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abstract = "With the advent of lanthanide-based technologies, there is a clear need to advance the fundamental understanding of 4f-element chelation chemistry. Herein, we contribute to a growing body of lanthanide chelation chemistry and report the synthesis of bimetallic 4f-element complexes within an imine/hemiacetalate framework, Ln2TPTOMe [Ln = lanthanide; TPTOMe = tris(pyridineimine)(Tren)tris(methoxyhemiacetalate); Tren = tris(2-aminoethylamine)]. These products are generated from hydrolysis and methanolysis of the cage ligand tris(pyridinediimine)bis(Tren) (TPT; Tadanobu et al. Chem. Lett. 1993, 22 (5), 859-862) likely facilitated by inductive effects stemming from the Lewis acidic lanthanide cations. These complexes are interesting because they result from imine cleavage to generate two metal binding sites: one pocketed site within the macrocycle and the other terminal site capping a hemiacetalate moiety. A clear demarcation in reactivity is observed between samarium and europium, where the lighter and larger lanthanides generate a mixture of products, Ln2TPTOMe and LnTPT. Meanwhile, the heavier and smaller lanthanides generate exclusively bimetallic Ln2TPTOMe. The cleavage reactivity to form Ln2TPTOMe was extended beyond methanol to include other primary alcohols.",

author = "Klamm, {Bonnie E.} and Albrecht-Schmitt, {Thomas E.} and Baumbach, {Ryan E.} and Billow, {Brennan S.} and White, {Frankie D.} and Kozimor, {Stosh A.} and Scott, {Brian L.} and Tondreau, {Aaron M.}",

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AU - White, Frankie D.

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AU - Scott, Brian L.

AU - Tondreau, Aaron M.

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Employing Lewis Acidity to Generate Bimetallic Lanthanide Complexes

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