Synthesis, structures and stereodynamic behavior of pentacoordinate (O-Si)-Chelate Difluoro(methyl)silylmethyl derivatives of amides and imides

Negrebetsky, V.V.; Kramarova, E.P.; Shipov, A.G.; Baukov, Y.I.; Korlyukov, A.A.; Arkhipov, D.E.; Bassindale, A.R.; Taylor, P.G.; Bylikin, S.Y.

Авторы: Negrebetsky Vadim V., Kramarova Eugeniya P., Shipov Aleksander G., Baukov Yuri I., Korlyukov Alexander A., Arkhipov Dmitry E., Bassindale Alan R., Taylor Peter G., Bylikin Sergey Yu
Журнал: Journal of Organometallic Chemistry
Том: 872
Год издания: 2018
Издательство: Elsevier BV
Местоположение издательства: Netherlands
Первая страница: 31
Последняя страница: 39
DOI: 10.1016/j.jorganchem.2018.07.027
Аннотация: The structures and stereodynamic behavior of (O -> Si)-chelate methyldifluorosilanes in solutions were studied by multinuclear (H-1, C-13, F-19, Si-29) and 2D (COSY, HETCOR H-1, C-13) NMR spectroscopy. The range of studied complexes included amides RC(O)N(R')CH2SiMeF2 [R = Ph, R' = H (1a); R = R' = Me (1b); R = Me, R' = CHMePh (1c)], lactams LCH2SiMeF2 (L = 2-oxoazepan-1-yl (2a), 2,2-dimethyl-4-oxo-2H-benzo[1,3] oxazin-3-yl (2b) or 4-methyl-2-oxoquinolin-l-yl (2c)] and the six-membered imide Im(6)CH(2) [2,6-dioxopiperidin-1-yl (3)]. The pentacoordination of silicon atoms in all studied compounds was confirmed by NMR study in solutions and single-crystal X-ray studies of complexes 1c, 2a, 2c and 3. The temperature dependency observed for the F-19 NMR signals in solution was explained by the ligand exchange in the coordination environment of silicon atoms (permutational isomerization) and used for determining the activation parameters of this process by F-19 DNMR. Quantum-chemical calculations for various isomers of complexes 1c, 2a, 2c and 3 suggested the "turnstile rotation" as the most likely mechanism for the observed stereodynamic processes.
Добавил в систему: Корлюков Александр Александрович

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Synthesis, structures and stereodynamic behavior of pentacoordinate (O-Si)-Chelate Difluoro(methyl)silylmethyl derivatives of amides and imidesстатья

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