التفاصيل البيبلوغرافية
العنوان: |
Au III Acyclic (Amino)(N-Pyridinium)carbenoids: Synthesis via Addition of 2-PySeCl to Au I -Bound Isonitriles, Structures, and Cytotoxicity. |
المؤلفون: |
Repina, Olga V., Kubasov, Alexey S., Vologzhanina, Anna V., Borisov, Alexander V., Kritchenkov, Ilya S., Voroshilkina, Ksenia M., Nazarov, Alexey A., Shchevnikov, Dmitriy M., Grudova, Mariya V., Gomila, Rosa M., Frontera, Antonio, Nenajdenko, Valentine G., Kritchenkov, Andreii S., Tskhovrebov, Alexander G. |
المصدر: |
International Journal of Molecular Sciences; Jan2025, Vol. 26 Issue 2, p483, 12p |
مصطلحات موضوعية: |
COUPLING reactions (Chemistry), ISOCYANIDES, NUCLEAR magnetic resonance spectroscopy, CYTOTOXINS, CISPLATIN, OXIDATIVE addition |
مستخلص: |
In this study, we report the first example of acyclic (amino)(N-pyridinium)carbenoid gold(III) complexes synthesized via a coupling reaction between 2-pyridylselenyl chloride and Au(I)-bound isonitriles. The reaction involves an initial oxidative addition of the Se–Cl moiety to Au(I), followed by the nucleophilic addition of the pyridine fragment to the isonitrile's C≡N bond, furnishing a metallacycle. Importantly, this is the first example of the pyridine acting as a nucleophile towards metal-bound isonitriles. Arguably, such an addition is due to the chelate effect. The structures of the gold(III) carbenoid complexes were unambiguously established using X-ray diffraction and NMR spectroscopy. Theoretical calculations, including DFT, Natural Resonance Theory (NRT), and Meyer bond order (MBO) analyses, were used to analyze the different resonance forms. The reaction mechanism was further elucidated using DFT calculations, which identified the oxidative addition as the rate-determining step with a barrier of 29.7 kcal/mol. The nucleophilic addition proceeds with a minimal barrier, making the reaction highly favorable. The antiproliferative activity of new compounds 2a–2e was tested against two human cancer cell lines: A2780 ovarian adenocarcinoma and the A278Cis cisplatin-resistant variant. [ABSTRACT FROM AUTHOR] |
|
Copyright of International Journal of Molecular Sciences is the property of MDPI and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) |
قاعدة البيانات: |
Complementary Index |