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Title: A Series of F-Element Chelators; Diaza Crown Ethers Functionalized with Catecholate Binding Substituents

Abstract

Here, we report on 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.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1412875
Alternate Identifier(s):
OSTI ID: 1548919
Report Number(s):
LA-UR-17-28162
Journal ID: ISSN 0022-328X; TRN: US1800387
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Organometallic Chemistry
Additional Journal Information:
Journal Volume: 857; Journal ID: ISSN 0022-328X
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and Physical Chemistry

Citation Formats

Stein, Benjamin W., Cary, Samantha K., Berg, John M., Birnbaum, Eva R., Kozimor, Stosh Anthony, Mocko, Veronika, and Scott, Brian Lindley. A Series of F-Element Chelators; Diaza Crown Ethers Functionalized with Catecholate Binding Substituents. United States: N. p., 2017. Web. doi:10.1016/j.jorganchem.2017.11.026.
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Stein, Benjamin W., Cary, Samantha K., Berg, John M., Birnbaum, Eva R., Kozimor, Stosh Anthony, Mocko, Veronika, & Scott, Brian Lindley. A Series of F-Element Chelators; Diaza Crown Ethers Functionalized with Catecholate Binding Substituents. United States. https://doi.org/10.1016/j.jorganchem.2017.11.026
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Stein, Benjamin W., Cary, Samantha K., Berg, John M., Birnbaum, Eva R., Kozimor, Stosh Anthony, Mocko, Veronika, and Scott, Brian Lindley. Wed . "A Series of F-Element Chelators; Diaza Crown Ethers Functionalized with Catecholate Binding Substituents". United States. https://doi.org/10.1016/j.jorganchem.2017.11.026. https://www.osti.gov/servlets/purl/1412875.
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@article{osti_1412875,
title = {A Series of F-Element Chelators; Diaza Crown Ethers Functionalized with Catecholate Binding Substituents},
author = {Stein, Benjamin W. and Cary, Samantha K. and Berg, John M. and Birnbaum, Eva R. and Kozimor, Stosh Anthony and Mocko, Veronika and Scott, Brian Lindley},
abstractNote = {Here, we report on 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.},
doi = {10.1016/j.jorganchem.2017.11.026},
journal = {Journal of Organometallic Chemistry},
number = ,
volume = 857,
place = {United States},
year = {Wed Dec 06 00:00:00 EST 2017},
month = {Wed Dec 06 00:00:00 EST 2017}
}
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