beta-donor interactions of exceptional strength in N,N-dimethylhydroxylaminochlorosilane, ClH2SiONMe2

Mitzel NW, Losehand U (1998)
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 120(29): 7320-7327.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
Download
Es wurden keine Dateien hochgeladen. Nur Publikationsnachweis!
Autor*in
Abstract / Bemerkung
The compounds ClH2SiONMe2 and ClH2SiONEt2 have been prepared by the reaction of the corresponding O-lithiated hydroxylamines and dichlorosilane. Their identity has been proved by gas-phase IR and solution NMR (H-1, C-13, N-15, O-17, and Si-29) spectroscopy. In contrast to CM2SiONMe2, ClH2SiONEt2 is unstable at ambient temperature and decomposes to give H2SiCl2 and H2Si(ONEt2)(2). ClH2SiONEt2 shows dynamic behavior in the solution as shown by low-temperature NMR. In the crystal ClH2SiONMe2 (low-temperature crystallography) is present as anti-conformer (torsional angle Cl-Si-O-N 180 degrees) and shows an exceptionally small Si-O-N angle of 79.7(1)degrees and a Si ... N distance of 2.028(1) Angstrom, corresponding to a relatively strong Si-N-beta-donor interaction. Ab initio calculations predict a wider Si-O-N angle of 91.6 degrees (MP2/6-311G**). A gas-phase structure determination by electron diffraction shows the presence of two conformers (anti and gauche), which are equal in potential energy. The Si-O-N angle in the anti-conformer is 87.1(9)degrees and that in the gauche-conformer 104.7(11)degrees [Cl-Si-O-N torsion angle: 72.9(28)degrees]. Calculations (MP2/6-31G*) have shown the angle Si-O-N and the energy of the system to be largely dependent on the torsion angle Cl-Si-O-N, with a variation of the angle Si-O-N over a range of 30 degrees during a full rotation of Cl-Si-O-N. Analysis of the calculated charges on the Si and N atoms show the beta-donor interaction not to be simply caused by electrostatic interaction. Natural bond orbital analysis describes a Ip-N --> sigma(Si-X)* type negative hyperconjugation as an important contribution to beta-donor bonding. The silicon substituent in anti position to nitrogen exerts the major effect on the strength of the beta-donor bond. Simultaneous analysis of negative hyperconjugation Ip-O --> sigma(Si-X)* shows the Si-O-N compounds to have similar contributions to this interaction as H3SiOCH3 and questions negative hyperconjugation to be quoted in isolation for the rationalization of the wide bond angles in silyl ethers.
Erscheinungsjahr
1998
Zeitschriftentitel
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Band
120
Ausgabe
29
Seite(n)
7320-7327
ISSN
0002-7863
eISSN
1520-5126
Page URI
https://pub.uni-bielefeld.de/record/1928921

Zitieren

Mitzel NW, Losehand U. beta-donor interactions of exceptional strength in N,N-dimethylhydroxylaminochlorosilane, ClH2SiONMe2. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. 1998;120(29):7320-7327.
Mitzel, N. W., & Losehand, U. (1998). beta-donor interactions of exceptional strength in N,N-dimethylhydroxylaminochlorosilane, ClH2SiONMe2. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 120(29), 7320-7327. https://doi.org/10.1021/ja980933j
Mitzel, Norbert W., and Losehand, U. 1998. “beta-donor interactions of exceptional strength in N,N-dimethylhydroxylaminochlorosilane, ClH2SiONMe2”. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 120 (29): 7320-7327.
Mitzel, N. W., and Losehand, U. (1998). beta-donor interactions of exceptional strength in N,N-dimethylhydroxylaminochlorosilane, ClH2SiONMe2. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 120, 7320-7327.
Mitzel, N.W., & Losehand, U., 1998. beta-donor interactions of exceptional strength in N,N-dimethylhydroxylaminochlorosilane, ClH2SiONMe2. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 120(29), p 7320-7327.
N.W. Mitzel and U. Losehand, “beta-donor interactions of exceptional strength in N,N-dimethylhydroxylaminochlorosilane, ClH2SiONMe2”, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 120, 1998, pp. 7320-7327.
Mitzel, N.W., Losehand, U.: beta-donor interactions of exceptional strength in N,N-dimethylhydroxylaminochlorosilane, ClH2SiONMe2. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. 120, 7320-7327 (1998).
Mitzel, Norbert W., and Losehand, U. “beta-donor interactions of exceptional strength in N,N-dimethylhydroxylaminochlorosilane, ClH2SiONMe2”. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 120.29 (1998): 7320-7327.
Export

Markieren/ Markierung löschen
Markierte Publikationen

Open Data PUB

Web of Science

Dieser Datensatz im Web of Science®
Suchen in

Google Scholar