A series of F-Element chelators; diaza crown ethers functionalized with catecholate binding substituents

Benjamin W. Stein; Samantha K. Cary; John M. Berg; Eva R. Birnbaum; Stosh A. Kozimor; Veronika Mocko; Brian L. Scott

doi:10.1016/j.jorganchem.2017.11.026

A series of F-Element chelators; diaza crown ethers functionalized with catecholate binding substituents

Benjamin W. Stein, Samantha K. Cary, John M. Berg, Eva R. Birnbaum, Stosh A. Kozimor, Veronika Mocko, Brian L. Scott

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

4 Scopus citations

Abstract

Reported here is the preparation of azacrown ethers functionalized with catechol groups. The synthetic approach was (1st) novel in that it made use of the Mannich reaction and (2nd) valuable in that it provided an improved synthesis (in terms of practical deployment) of the known N,N′-bis(2,3-dihydroxybenzyl)-4,13-diaza-18-crown-6, H₄ChaCha. Moreover, it demonstrated potential application of the synthetic method for accommodating a wide range of catecholate functionalities by using the synthetic strategy to prepare N,N′-bis(2,3-dihydroxy-5-tert-butylbenzyl)-4,13-diaza-18-crown-6 (H₄^tBu₂ChaCha) for the first time. These H₄ChaCha and H₄^tBu₂ChaCha macrocycles offer exciting opportunity to expand redox chemistry for the f-elements. As “proof-of-principle,” we isolated the unusual tetrameric cluster [La₂(^tBuChaCha)₂]₂ from reactions between H₄^tBu₂ChaCha and La[N(SiMe₃)₂]₃. Characterization of [La₂(^tBuChaCha)₂]₂ by elemental analysis, single crystal X-ray diffraction, IR, and UV–vis–NIR spectroscopy suggested that the complex represented a rare example of an f-element semiquinone. It further demonstrated that the combination of La³⁺ and H₄^tBu₂ChaCha provided access to one-electron oxidation chemistry within redox potential windows that were amenable to mild reaction conditions.

Original language	English
Pages (from-to)	170-179
Number of pages	10
Journal	Journal of Organometallic Chemistry
Volume	857
DOIs	https://doi.org/10.1016/j.jorganchem.2017.11.026
State	Published - Feb 15 2018
Externally published	Yes

Funding

We gratefully recognize the Heavy Element Chemistry Program at LANL by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy (Kozimor, Mocko, Scott) and the LANL LDRD program (Berg, Birnbaum). Los Alamos National Laboratory is operated by Los Alamos National Security, LLC, for the National Nuclear Security Administration of U.S. Department of Energy (contract DE-AC52-06NA25396). Portions of this work were supported by postdoctoral fellowships from the Glenn T. Seaborg Institute (Stein) and the LDRD office , named fellowship program; Marie Curie Distinguished Postdoctoral Fellowship (Cary).

Funders	Funder number
Glenn T. Seaborg Institute
LANL LDRD
Office of Basic Energy Sciences
U.S. Department of Energy
Chemical Sciences, Geosciences, and Biosciences Division

Keywords

Catechol
Crown ether
Lanthanide

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10.1016/j.jorganchem.2017.11.026

Cite this

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title = "A series of F-Element chelators; diaza crown ethers functionalized with catecholate binding substituents",

abstract = "Reported here is the preparation of azacrown ethers functionalized with catechol groups. The synthetic approach was (1st) novel in that it made use of the Mannich reaction and (2nd) valuable in that it provided an improved synthesis (in terms of practical deployment) of the known N,N′-bis(2,3-dihydroxybenzyl)-4,13-diaza-18-crown-6, H4ChaCha. Moreover, it demonstrated potential application of the synthetic method for accommodating a wide range of catecholate functionalities by using the synthetic strategy to prepare N,N′-bis(2,3-dihydroxy-5-tert-butylbenzyl)-4,13-diaza-18-crown-6 (H4tBu2ChaCha) for the first time. These H4ChaCha and H4tBu2ChaCha macrocycles offer exciting opportunity to expand redox chemistry for the f-elements. As “proof-of-principle,” we isolated the unusual tetrameric cluster [La2(tBuChaCha)2]2 from reactions between H4tBu2ChaCha and La[N(SiMe3)2]3. Characterization of [La2(tBuChaCha)2]2 by elemental analysis, single crystal X-ray diffraction, IR, and UV–vis–NIR spectroscopy suggested that the complex represented a rare example of an f-element semiquinone. It further demonstrated that the combination of La3+ and H4tBu2ChaCha provided access to one-electron oxidation chemistry within redox potential windows that were amenable to mild reaction conditions.",

keywords = "Catechol, Crown ether, Lanthanide",

author = "Stein, {Benjamin W.} and Cary, {Samantha K.} and Berg, {John M.} and Birnbaum, {Eva R.} and Kozimor, {Stosh A.} and Veronika Mocko and Scott, {Brian L.}",

note = "Publisher Copyright: {\textcopyright} 2017",

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AU - Stein, Benjamin W.

AU - Cary, Samantha K.

AU - Berg, John M.

AU - Birnbaum, Eva R.

AU - Kozimor, Stosh A.

AU - Mocko, Veronika

AU - Scott, Brian L.

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N2 - Reported here is the preparation of azacrown ethers functionalized with catechol groups. The synthetic approach was (1st) novel in that it made use of the Mannich reaction and (2nd) valuable in that it provided an improved synthesis (in terms of practical deployment) of the known N,N′-bis(2,3-dihydroxybenzyl)-4,13-diaza-18-crown-6, H4ChaCha. Moreover, it demonstrated potential application of the synthetic method for accommodating a wide range of catecholate functionalities by using the synthetic strategy to prepare N,N′-bis(2,3-dihydroxy-5-tert-butylbenzyl)-4,13-diaza-18-crown-6 (H4tBu2ChaCha) for the first time. These H4ChaCha and H4tBu2ChaCha macrocycles offer exciting opportunity to expand redox chemistry for the f-elements. As “proof-of-principle,” we isolated the unusual tetrameric cluster [La2(tBuChaCha)2]2 from reactions between H4tBu2ChaCha and La[N(SiMe3)2]3. Characterization of [La2(tBuChaCha)2]2 by elemental analysis, single crystal X-ray diffraction, IR, and UV–vis–NIR spectroscopy suggested that the complex represented a rare example of an f-element semiquinone. It further demonstrated that the combination of La3+ and H4tBu2ChaCha provided access to one-electron oxidation chemistry within redox potential windows that were amenable to mild reaction conditions.

AB - Reported here is the preparation of azacrown ethers functionalized with catechol groups. The synthetic approach was (1st) novel in that it made use of the Mannich reaction and (2nd) valuable in that it provided an improved synthesis (in terms of practical deployment) of the known N,N′-bis(2,3-dihydroxybenzyl)-4,13-diaza-18-crown-6, H4ChaCha. Moreover, it demonstrated potential application of the synthetic method for accommodating a wide range of catecholate functionalities by using the synthetic strategy to prepare N,N′-bis(2,3-dihydroxy-5-tert-butylbenzyl)-4,13-diaza-18-crown-6 (H4tBu2ChaCha) for the first time. These H4ChaCha and H4tBu2ChaCha macrocycles offer exciting opportunity to expand redox chemistry for the f-elements. As “proof-of-principle,” we isolated the unusual tetrameric cluster [La2(tBuChaCha)2]2 from reactions between H4tBu2ChaCha and La[N(SiMe3)2]3. Characterization of [La2(tBuChaCha)2]2 by elemental analysis, single crystal X-ray diffraction, IR, and UV–vis–NIR spectroscopy suggested that the complex represented a rare example of an f-element semiquinone. It further demonstrated that the combination of La3+ and H4tBu2ChaCha provided access to one-electron oxidation chemistry within redox potential windows that were amenable to mild reaction conditions.

KW - Catechol

KW - Crown ether

KW - Lanthanide

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JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

A series of F-Element chelators; diaza crown ethers functionalized with catecholate binding substituents

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Keywords

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