METHYLSILYLHYDROXYLAMINES - PREPARATIVE, SPECTROSCOPIC AND AB-INITIO STUDIES

Mitzel NW, HOFMANN M, WATERSTRADT E, SCHLEYER PV, SCHMIDBAUR H (1994)
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS (17): 2503-2508.

Journal Article | Published | English

No fulltext has been uploaded

Author
; ; ; ;
Abstract
Methylsilylhydroxylamines [(MeH2Si)2NOMe, (MeH2Si)MeNOMe, Me2NOSiH2Me] have been prepared from bromo(methyl)silane and the corresponding methylhydroxylamines in the presence of an auxiliary base (triethylamine or N,N,N',N'-tetramethylethylenediamine). The compounds were studied by NMR spectroscopy of all elements present (H-1, C-13, N-15, O-17, Si-29). The magnitude of the one-bond coupling constants (J(NSi))-J-1-N-15-Si-29 is interpreted in terms of the hybridization associated with the pyramidal co-ordination of nitrogen, a unique structural feature in Si/N chemistry. Ab initio studies confirmed these structural predictions. Singly silylated hydroxylamines have been shown to be more strongly pyramidal than doubly silylated ones. Calculations on the model compound (H3Si)2NOMe gave a barrier to inversion at nitrogen of 9.7 kcal mol-1. This inversion is accompanied by a partial rotation around the N-O bond. The NMR chemical shifts of the compounds have been calculated and the results are in good agreement with the experimental data. The unusually low chemical shifts delta(O-17) of hydroxylamines have thus been confirmed by theory. A comparison of the calculated normal modes of vibration with experimental data leads to a complete assignment of the IR spectra.
Publishing Year
ISSN
eISSN
PUB-ID

Cite this

Mitzel NW, HOFMANN M, WATERSTRADT E, SCHLEYER PV, SCHMIDBAUR H. METHYLSILYLHYDROXYLAMINES - PREPARATIVE, SPECTROSCOPIC AND AB-INITIO STUDIES. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS. 1994;(17):2503-2508.
Mitzel, N. W., HOFMANN, M., WATERSTRADT, E., SCHLEYER, P. V., & SCHMIDBAUR, H. (1994). METHYLSILYLHYDROXYLAMINES - PREPARATIVE, SPECTROSCOPIC AND AB-INITIO STUDIES. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS(17), 2503-2508.
Mitzel, N. W., HOFMANN, M., WATERSTRADT, E., SCHLEYER, P. V., and SCHMIDBAUR, H. (1994). METHYLSILYLHYDROXYLAMINES - PREPARATIVE, SPECTROSCOPIC AND AB-INITIO STUDIES. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2503-2508.
Mitzel, N.W., et al., 1994. METHYLSILYLHYDROXYLAMINES - PREPARATIVE, SPECTROSCOPIC AND AB-INITIO STUDIES. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, (17), p 2503-2508.
N.W. Mitzel, et al., “METHYLSILYLHYDROXYLAMINES - PREPARATIVE, SPECTROSCOPIC AND AB-INITIO STUDIES”, JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1994, pp. 2503-2508.
Mitzel, N.W., HOFMANN, M., WATERSTRADT, E., SCHLEYER, P.V., SCHMIDBAUR, H.: METHYLSILYLHYDROXYLAMINES - PREPARATIVE, SPECTROSCOPIC AND AB-INITIO STUDIES. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS. 2503-2508 (1994).
Mitzel, Norbert W., HOFMANN, M, WATERSTRADT, E, SCHLEYER, PV, and SCHMIDBAUR, H. “METHYLSILYLHYDROXYLAMINES - PREPARATIVE, SPECTROSCOPIC AND AB-INITIO STUDIES”. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS 17 (1994): 2503-2508.
This data publication is cited in the following publications:
This publication cites the following data publications:

Export

0 Marked Publications

Open Data PUB

Web of Science

View record in Web of Science®

Search this title in

Google Scholar