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

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

doi:10.1016/j.jorganchem.2017.11.026

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

Journal Article · Wed Dec 06 00:00:00 EST 2017 · Journal of Organometallic Chemistry

DOI:https://doi.org/10.1016/j.jorganchem.2017.11.026· OSTI ID:1412875

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Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

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 (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.

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Research Organization:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1412875

Alternate ID(s):: OSTI ID: 1548919

Report Number(s):: LA-UR-17-28162; TRN: US1800387

Journal Information:: Journal of Organometallic Chemistry, Vol. 857; ISSN 0022-328X

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 2 works

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

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