G.E. Herberich et al. / Journal of Organometallic Chemistry 567 (1998) 127–131
131
4
.4. The N,N%,N¦-trimethyl-hexahydro-1,3,5-triazine
gence was obtained for 307 parameters with the agree-
(TMHT) sol6ate [Li(TMHT)][C H B(NMe ) ] (4)
ment factors R=0.058 and R =0.071, using statistical
9
6
2 2
w
2
weights w=1/| (F ). The final difference fourier map
0
Salt Li(3) (0.26 g, 1.19 mmol) was dissolved in ether
10 ml). Dropwise addition of TMHT (0.18 g, 1.39
showed a maximum of residual electron density of
−
6
−3
(
0.253 · 10
e pm
[16].
mmol) and cooling to −30°C gave 4 as large colorless
crystals. Anal. Found: C, 65.53; H, 9.48; N, 19.40.
C H BLiN Calc.: C,65.15; H, 9.78; N, 19.99%.
Acknowledgements
1
9
33
5
This work was generously supported by the Fonds
der Chemischen Industrie.
4
.5. Lithium [1-(4,4,5,5-tetramethyl-1,3,2-dioxaboro-
lan-2-yl)indenide (Li(5))
Compound 2 (2.90 g, 11.93 mmol) in hexane (30 ml)
was added dropwise to a stirred solution of LiN(-
SiMe ) [13] (2.01 g, 11.93 mmol) in hexane (40 ml) at
References
3
2
[
1] Presented at GECOM CONCORD 97, May 19–23, 1997: G.E.
Herberich, E. Barday, B. Frange, B. Gautheron, Synth e` se et
M e´ tallation de Ligandes Ind e´ nylboranes.
−
78°C. After the solution had warmed up to ambient
temperature, the salt was transferred onto a frit and
washed twice with hexane. Drying in a vacuum gave
Li(5) (2.48 g, 85%) as a white powder, highly sensitive
to air and humidity. LiTMP, LDA and LiInd can also
[2] G.E. Herberich, A. Fischer, Organometallics 15 (1996) 58.
[
3] (a) B.M. Mikhailov, T.K. Baryshnikova, V.S. Bogdanov, Zh.
Obshch. Khim. 43 (1973) 1949. (b) Chem. Abstr. 80 (1974)
3
566b. (c) D. Duchateau, S.J. Lancaster, M. Thornton-Pett, M.
be used as base.
Bochmann, Organometallics 16 (1997) 4995.
1
H NMR (THF-d ): l=1.25 (s, 2 CMe ), 6.01 (dd,
8
3
2
[4] A. Mendoza, D.S. Matteson, J. Organomet. Chem. 156 (1978)
149.
4
23 34 6 4
3
-H), 6.96 (d, 2-H), J =3.5, J =0.6 Hz, C H : 6.49
[
5] W.R. Roth, Tetrahedron Lett. (1964) 1009.
[6] (a) G. Bergson, A.-M. Weidler, Acta Chem. Scand. 17 (1963)
798. (b) A.-M. Weidler, Acta Chem. Scand. 17 (1963) 2724. (c)
(
1m, 1H), 6.54 (tm, 1H), 7.27 (dm, 1H), 7.82 (dm, 1H).
1
3
C NMR (THF-d ): l=25.78 (Me), 80.97 (CO), C-1
8
1
not observed, 98.50 (C-3), 115.14, 115.52, 119.10,
J. Almy, R.T. Uyeda, D.J. Cram, J. Am. Chem. Soc. 89 (1967)
6768.
1
1
1
22.22, 126.98, 134.19, 138.43. B NMR (160 MHz,
[
7] For leading references see: C.E. Housecroft, in: E.W. Abel,
F.G.A. Stone, Wilkinson (Eds.), Comprehensive Organometallic
Chemistry II, vol. 1, Pergamon, Oxford, 1995, p. 129.
8] A.J. Ashe III, P. Shu, J. Am. Chem. Soc. 93 (1971) 1804.
9] (a) M.W. Rathke, R. Kow, J. Am. Chem. Soc. 94 (1972) 6854.
(b) R. Kow, M.W. Rathke, J. Am. Chem. Soc. 95 (1973) 2715.
THF-d ): l=30.5.
8
4.6. X-ray structure determination of 4
[
[
−
1
C H BLiN molecular weight 349.3 g mol , tri-
1
9
33
5
[
[
10] G.E. Herberich, B. Schmidt, U. Englert, Organometallics 14
1995) 471.
11] L. Brandsma, in: Preparative Polar Organometallic Chemistry 2,
Springer Verlag, Berlin, 1990, p. 45.
clinic,
P
(
No. 2), a=838.4(5), b=1025.6(3), c=
(
1306.2(2) pm, h=103.67(2), i=94.95(4), k=96.91(4)°,
3
−3
Z=2, V=1.076(1) nm , dcalc=1.078 g cm , (Mo–
K =0.6017 cm , F(000)=380.0. Diffraction data
−
1
h
[12] M. Fieser, L.F. Fieser, Reagents for Organic Synthesis, vol. 4,
Wiley Interscience, New York, 1974, p. 310.
were collected with an ENRAF-Nonius CAD4-diffrac-
tometer at 203 K, Mo–Kh radiation (graphite
monochromator, u=71.07 pm), colorless crystal
[
13] (a) M.W. Rathke, Org. Synth. Coll. 6 (1988) 598. (b) E.H.
Amonoo-Neizer, R.A. Shaw, D.O. Skovlin, B.C. Smith, Inorg.
Synth. 8 (1966) 19.
(
(
needle), crystal size 0.3×0.4×0.8 mm, ꢀ-2U scans
3BUB28°). All data were corrected for Lorentz and
[
14] B.A. Frenz, The ENRAF-Nonius CAD4-SDP—a real-time sys-
tem for concurrent X-ray data collection and crystal structure
determination, in: H. Schenk, R. Olthof-Hazekamp, H. van
Koningsveld, G.C. Bassi (Eds.), Computing in Crystallography,
Delft University Press, Delft 1978; SDP-PLUS, Version 1.1
polarization effects, using the SDP system of programs
14]. Of the 6128 data collected, 2736 were unique with
[
intensities I\1 |(I) and only those were used in the
structure solution and refinement. The structure was
solved by direct methods (SHELXS-86) [15] and differ-
ence fourier maps. The hydrogen atoms were refined
isotropically, except the ones in the triazane ligand.
Those hydrogen atoms were treated as riding with
isotropic thermal parameters of B =1.3 · B . Conver-
(
1984) and VAXSDP, Version 2.2 (1985).
[15] G.M. Sheldrick, SHELXS-86, program for crystal structure de-
termination, G o¨ ttingen, 1986.
[
16] Further details of the crystal structure analysis are available on
request from the Fachinformationszentrum Karlsruhe,
Gesellschaft f u¨ r wissenschaftlich-technische Information mbH,
D-76344 Eggenstein-Leopoldshafen, on quoting the depository
number CSD-408273.
H
C
.