Strong intramolecular secondary Si center dot center dot center dot N bonds in trifluorosilylhydrazines

Vojinovic K, McLachlan LI, Hinchley SL, Rankin DWH, Mitzel NW (2004)
CHEMISTRY-A EUROPEAN JOURNAL 10(12): 3033-3042.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
The simple silylhydrazines F3SiN(Me)NMe2 (1), FSi(N(Me)NMe2)(2) (2), and F3SiN(SiMe3)NMe2 (3) have been prepared by reaction of SiF4 with LiN(Me)NMe2 and LiN(SiMe3)NW2, while F3SiN(SnMe3)NMe2 (4) was prepared from SiF4 and (Me3Sn)(2)NNMe2 (5). The compounds were characterized by gas-phase IR and multinuclear NMR spectroscopy (H-1, C-13, N-14/15, F-19, Si-29, Sn-119), as well as by mass spectrometry. The crystal structures of compounds 1-5 were determined by X-ray crystallography. The structures of free molecules I and 3 were determined by gas-phase electron diffraction. The structures of 1, 2, and 4 were also determined by ab initio calculations at the MP2/6-311 + G** level of theory. These structural studies constitute the first experimental proof for the presence of strong Si...N beta-donor-acceptor bonds between the SiF3 and geminal NMe2 groups in silylhydrazines. The strength of these non-classical Si...N interactions is strongly dependent on the nature of the substituent at the alpha-nitrogen atom of the SiNN unit, and has the order 3>4>1. The valence angles at these extremely deformed alpha-nitrogen atoms, and the Si...N distances are (crystal/gas): 1 104.2(1)/106.5(4)degrees, 2.438(1)/2.510(6) Angstrom; 3 83.6(1)/84.9(4)degrees, 2.102(1)/2.135(9) Angstrom; 4 89.6(1)', 2.204(2) Angstrom.
Stichworte
hydrazines; donor bonds; crystal structure; electron diffraction; silicon
Erscheinungsjahr
2004
Zeitschriftentitel
CHEMISTRY-A EUROPEAN JOURNAL
Band
10
Ausgabe
12
Seite(n)
3033-3042
ISSN
0947-6539
eISSN
1521-3765
Page URI
https://pub.uni-bielefeld.de/record/1928683

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Vojinovic K, McLachlan LI, Hinchley SL, Rankin DWH, Mitzel NW. Strong intramolecular secondary Si center dot center dot center dot N bonds in trifluorosilylhydrazines. CHEMISTRY-A EUROPEAN JOURNAL. 2004;10(12):3033-3042.
Vojinovic, K., McLachlan, L. I., Hinchley, S. L., Rankin, D. W. H., & Mitzel, N. W. (2004). Strong intramolecular secondary Si center dot center dot center dot N bonds in trifluorosilylhydrazines. CHEMISTRY-A EUROPEAN JOURNAL, 10(12), 3033-3042. doi:10.1002/chem.200400069
Vojinovic, K., McLachlan, L. I., Hinchley, S. L., Rankin, D. W. H., and Mitzel, N. W. (2004). Strong intramolecular secondary Si center dot center dot center dot N bonds in trifluorosilylhydrazines. CHEMISTRY-A EUROPEAN JOURNAL 10, 3033-3042.
Vojinovic, K., et al., 2004. Strong intramolecular secondary Si center dot center dot center dot N bonds in trifluorosilylhydrazines. CHEMISTRY-A EUROPEAN JOURNAL, 10(12), p 3033-3042.
K. Vojinovic, et al., “Strong intramolecular secondary Si center dot center dot center dot N bonds in trifluorosilylhydrazines”, CHEMISTRY-A EUROPEAN JOURNAL, vol. 10, 2004, pp. 3033-3042.
Vojinovic, K., McLachlan, L.I., Hinchley, S.L., Rankin, D.W.H., Mitzel, N.W.: Strong intramolecular secondary Si center dot center dot center dot N bonds in trifluorosilylhydrazines. CHEMISTRY-A EUROPEAN JOURNAL. 10, 3033-3042 (2004).
Vojinovic, K, McLachlan, LI, Hinchley, SL, Rankin, DWH, and Mitzel, Norbert W. “Strong intramolecular secondary Si center dot center dot center dot N bonds in trifluorosilylhydrazines”. CHEMISTRY-A EUROPEAN JOURNAL 10.12 (2004): 3033-3042.

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