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Preparation and structural characterization of [K(18-crown-6)]+ salts of [RNSN]- anions and the [NSN]2- dianion Научная публикация

Журнал European Journal of Inorganic Chemistry
ISSN: 1434-1948 , E-ISSN: 1099-0682
Вых. Данные Год: 2004, Номер: 12, Страницы: 2452-2458 Страниц : 7 DOI: 10.1002/ejic.200300954
Ключевые слова Nitrogen; NMR spectroscopy; Sulfur; X-ray diffraction
Авторы Borrmann T. 1 , Lork E. 1 , Mews R. 2 , Shakirov M.M. 3 , Zibarev A.V. 3
Организации
1 (Scopus) Institute of Organic Chemistry, NW2 C, University of Bremen, 28334 Bremen, Germany
2 (Scopus) Inst. for Inorg. and Phys. Chemistry, NW2 C, University of Bremen, 28334 Bremen, Germany
3 (Scopus) Institute of Organic Chemistry, Russian Academy of Sciences, 630090 Novosibirsk, Russian Federation

Реферат: [K(18-crown-6)]+ salts of the [RNSN]- anions (R = Alk, Ar) and the [NSN]2- dianion, which are thermally stable and very soluble in aprotic organic solvents, were prepared from [K(18-crown-6)] +[tBuO]- and the corresponding R-N=S= N-SiMe3 and (Me3Si-N=)2S, respectively. The salts are characterized by multinuclear (1H, 13C, 14N, 19F, 29Si and 39K) NMR spectroscopy in solution and by X-ray diffraction in the solid state. The experimentally determined bond lengths confirm that the [RNSN]- anions are thiazylamides, R-N --S≡N rather than sulfur diimides, R-N=S=N-. Relative to O=S=O, in the [NSN]2- dianion, which is the genuine aza-analogue of sulfur dioxide, the bond lengths are elongated and the bond angle is widened. This might reflect electrostatic repulsion between the negatively charged N atoms. The experimental results are in agreement with theoretical calculations (RHF, B3LYP, MP2). In the nitrogen NMR spectra, when going from [AlkNSN]- to [ArNSN]-, the low-field signal of the terminal (unsubstituted) N atom reveals further deshielding, whereas the high-field signal of the internal (substituted) N atom displays further shielding. The 14N NMR resonance for the [NSN]2- dianion is practically insensitive to the counterion. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
Библиографическая ссылка: Borrmann T. , Lork E. , Mews R. , Shakirov M.M. , Zibarev A.V.
Preparation and structural characterization of [K(18-crown-6)]+ salts of [RNSN]- anions and the [NSN]2- dianion
European Journal of Inorganic Chemistry. 2004. N12. P.2452-2458. DOI: 10.1002/ejic.200300954 WOS Scopus РИНЦ OpenAlex
Даты:
Опубликована в печати: 1 июн. 2004 г.
Идентификаторы БД:
Web of science: WOS:000222330800008
Scopus: 2-s2.0-4544275328
РИНЦ: 13471830
OpenAlex: W1970412597
Цитирование в БД:
БД Цитирований
Scopus 18
Web of science 17
OpenAlex 21
Альметрики: