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H. Nöth - H. Sachdev • Contribution to the Chemistry of Boron, 241
to attain ambient temperature, the 11B NMR spectrum of
[Me3SiN(H)-BCl2]2; 6.0 CbB-NH(SiMe3)2; 30.6
the solution showed resonances for (C1B=NH)3 (<5n B =
30.6, 75%) and monomeric Cl2B-N(H)SiMe3 {b = 38.6.
25%) as well as of [Me3SiN(H)-BCl2]2 (b = 4.6 ~ 4%).
After heating to reflux the solid disappeared with forma-
(C1B=NH)3; 38.6 Me^SiNKfO-BCK If there was some
Me;?SiN(H)-BCl2 remaining in the solution, it could be
decomposed to (C1B =NH)3 by heating to reflux. All
volatile compounds were removed after 6 h in a vacuum.
The oily residue crystallized completely after 2d and con- tion of (C1B=NH)3. All volatiles were then removed in
sisted of pure trichloroborazine (<5'1B = 30.6). Yield: 78g
(96%).
vacuo. The yield was comparable to that of the previous
method (74g, 93%). Purification by sublimation was not
d) When the same reaction was performed at -78 °C. a necessary.
large amount of a white precipitate was formed on adding
BCI3, and the amount of Me3SiCl according to the NMR
spectra (<5:9Si = 30,5) was very small after the addition
e)
If the reaction was performed stoichiometrically un-
der analogous conditions [10 ml of BCI3 (0,133 mol),
28,3 ml ofHN(SiMe3)2(0,133 mol), 200 ml of hexane], a
was completed. The 11B NMR spectrum exhibited a sig- large amount of a white precipitate was formed. Although
the mixture was heated to reflux for 6h, only 2,6 g (34%)
of trichloroborazine was isolated by sublimation.
nal at b = 38,6 due to Cl2B-N(H)SiMe3) besides a large
signal due to BCl3(6 = 46). After the solution was allowed
b) C. Brown, A. W. Laubengayer, J. Am. Chem.
Soc. 72, 3699 (1955).
[1] Contribution 240: B. Kaufmann, R. Jetzfellner,
K. Issleib, E. Leissring, H. Nöth, M. Schmidt, Chem.
Ber., submitted.
[2] a) PhD Thesis H. Sachdev, University of Munich
(1995);
[8] H. Nöth. Z. Naturforsch. 16b, 618 (1961).
[9] H. Nöth. B. Wrackmeyer, Nuclear Magnetic Res-
onance Spectroscopy of Boron Compounds, Vol.
14 of the Series '‘NMR. Basis Principles and
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Springer Publishers. Berlin, Heidelberg, New York
(1978).
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b) a yield of 88% is reported when NH4CI was
reacted with BCI3 in boiling toluene.
[11] PhD Thesis, T. Gasparis-Ebeling, University of Mu-
nich (1984).
[12] M. Butcher, W. Gerrard, J. Inorg. Nucl. Chem. 27,
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b) Gmelin, Handbuch der Anorg. Chem. Vol. 13,
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[4] R. Schaeffer, M. Steindler, L. Holmstedt. H. Smith,
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[6 ] T. Widemann, L. G. Sneddon. Inorg. Chem. 34. 1002
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[14] Gmelin. Handbuch der Anorg. Chemie, Vol. 22,
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Publishers, Berlin, Heidelberg, New York (1975).
According to the procedure described in Lit. [10]
toluene is obviously a better solvent than chloro-
benzene.
[15] H. S. Turner, R. J. Warne, J. Chem. Soc. 6421
(1965).
[7] a) A. W. Laubengayer. P. C. Moews. R. F. Porter,
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