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Chlorinated Cubane-1,4-dicarboxylic Acids
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SYSNO ASEP 0568796 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Ostatní články Název Chlorinated Cubane-1,4-dicarboxylic Acids Tvůrce(i) Křížková, Adéla (UOCHB-X)
Bastien, Guillaume (UOCHB-X) ORCID
Rončević, Igor (UOCHB-X) ORCID, RID
Císařová, I. (CZ)
Rybáček, Jiří (UOCHB-X) RID, ORCID
Kašička, Václav (UOCHB-X) RID, ORCID
Kaleta, Jiří (UOCHB-X) RID, ORCIDZdroj.dok. Journal of Organic Chemistry. - : American Chemical Society - ISSN 0022-3263
(2024)Poč.str. 9 s. Jazyk dok. eng - angličtina Země vyd. US - Spojené státy americké Klíč. slova basis-sets ; cubane ; electron Obor OECD Organic chemistry CEP GA20-13745S GA ČR - Grantová agentura ČR LTAUSA19120 GA MŠMT - Ministerstvo školství, mládeže a tělovýchovy Výzkumná infrastruktura e-INFRA CZ - 90140 - CESNET, zájmové sdružení právnických osob Způsob publikování Open access Institucionální podpora UOCHB-X - RVO:61388963 DOI 10.1021/acs.joc.2c02872 Anotace Herein, we report radical chlorination of cubane-1,4-dicarboxylic acid leading preferentially to one monochlorinated cubane dicarboxylate (ca. 70%) that is accompanied by four dichlorinated derivatives (ca. 20% in total). The exact positions of the chlorine atoms have been confirmed by X-ray diffraction of the corresponding single crystals. The acidity constants of all dicarboxylic acids in water were determined by capillary electrophoresis (3.17 ± 0.04 and 4.09 ± 0.05 for monochlorinated and ca. 2.71 ± 0.05 and 3.75 ± 0.05 for dichlorinated cubanes). All chlorinated derivatives as well as the parent diacid showed high thermal stability (decomposition above 250 °C) as documented by differential scanning calorimetry. The probable reaction pathways leading to individual isomers were proposed, and the energies of individual transition states and intermediates were obtained using density functional theory calculations (B3LYP-D3BJ/6-311+G(d,p)). The relative strain energies for all newly prepared derivatives as well as for hypothetical hexahalogenated (fluorinated, chlorinated, brominated, and iodinated) derivatives of cubane-1,4-dicarboxylic acids were predicted using wavefunction theory methods. The hexafluorinated derivative was identified as the most strained compound (57.5 kcal/mol), and the relative strain decreased as the size of halogen atoms increased (23.7 for hexachloro, 16.7 for hexabromo, and 4.0 kcal/mol for the hexaiodo derivative). Pracoviště Ústav organické chemie a biochemie Kontakt asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418 Rok sběru 2025 Elektronická adresa https://doi.org/10.1021/acs.joc.2c02872
Počet záznamů: 1