U. Klingebiel et al.
system had been heated at reflux for 2 h, the lithium anilide was dis-
solved in THF (100 mL) and slowly added variously to di(isopropyl)ami-
no-difluoroborane (7, 10, 11), to diACTHNUTRGNE(NUG isobutyl)amino-difluoroborane (8, 12)
Compounds 13, 15 and 16: A solution of trichloroalane (0.1 mol) in di-
ethyl ether (50 mL) was added at ꢀ208C to a solution either of 11
(0.1 mol) in diethyl ether (100 mL) or of 12 (0.1 mol) in diethyl ether
(50 mL) and dichloromethane (50 mL), and the mixture was stirred for
4 h at 08C. Compounds 13 and 15 were crystallised from diethyl ether at
08C and 16 at room temperature.
or to (trimethylsilyl)methylamino-difluoroborane (9[13]) (0.2 mol) and the
mixture was heated to reflux for 3 h. The crude product was separated
from LiF by condensation of the volatile components into a cooling trap
in vacuo. Compounds 7–12 were purified by distillation and recrystallisa-
tion from n-hexane.
Di(isopropyl)amine-2,6-di(isopropyl)anilino-n-butyl-borenium tetrachlor-
oaluminate (13): Yield 20%; decomposition at 258C.
Di(isopropyl)amino-2,6-di(isopropyl)anilino-fluoroborane
(7):
Yield
DiACTHNUTRGENUG(N isobutyl)amine-[(N-dimethylfluorosilyl)-2,6-di(isopropyl)anilino)]-
97%; m.p. 838C; b.p. 708C (0.01 mbar); 1H NMR (CDCl3): d=1.19 (d,
methylborenium tetrachloroaluminate (15): Yield 18%; decomposition at
3
3JH,H =6.8 Hz, 12H; C CHMe2), 1.19 (d, JH,H =6.8 Hz, 12H; N CHMe2),
388C; MS (EI): m/z (%): 407 [MꢀAlCl4]+ (10), 278 [MꢀNH
ACHTUNGTRENNUNG
(iBu)2]+
ꢀ
ꢀ
3.27 (sept, 3JH,H =6.8 Hz, 2H; C CHMe2), 3.37 (sept, 3JH,H =6.8 Hz, 2H;
ꢀ
(30).
N CHMe2), 3.39 (d, 3JH,F =0.6 Hz, 1H; NH), 7.02–7.11 ppm (m, 3H;
ꢀ
DiACTHNUTRGNEUNG
(isobutyl)amine aluminium (16): M.p. 778C; 1H NMR (CDCl3): d=
13
ꢀ
ꢀ
arom. CH); C NMR (CDCl3): d=22.43 (N CHMe2), 23.40 (C CHMe2),
1.06 (d, 3JH,H =6.7 Hz, 12H; CHMe2), 2.19 (m, 2H; CHMe2), 2.94 ppm
(m, 4H; CH2); 13C NMR (CDCl3): d=20.24 (CHMe2), 25.63 (CHMe2),
56.04 ppm (CH2); 27Al NMR (CDCl3): d=103.41 ppm.
ꢀ
ꢀ
28.51 (C CHMe2), 44.58 (N CHMe2), 122.88 (m-C), 125.10 (p-C), 132.43
(o-C), 145.11 ppm (i-C); 11B NMR (CDCl3): d=21.78 ppm; 19F NMR
(CDCl3): d=28.98 ppm; MS (EI): m/z (%): 306 [M]+ (20), 205 (100)
Crystal structure determination: Single crystals were selected from
Schlenk flasks under argon and covered with perfluorated polyether oil
on a microscope slide, which in the case of 6 was cooled with a nitrogen
gas flow by use of the X-TEMP 2.[24] Suitable crystals were mounted on
the tip of a glass fibre fixed to a goniometer head and shock-cooled with
the crystal cooling device. All data were collected with use of monochro-
mated MoKa radiation (l=71.073 pm) variously with a Bruker TXS rotat-
ing anode (6), a Bruker Smart Apex II with D8 goniometer (7, 9, 10, 11)
or a Stoe IPDS II with image plate detector (13, 16).
[MꢀN
Di(isobutyl)amino-2,6-di(isopropyl)anilino-fluoroborane (8): Yield 95%;
m.p. 818C; b.p. 808C (0.01 mbar); 1H NMR (CDCl3): d=0.91 (d, JH,H
ACHTUNGTRENNUNG
(CHMe2)2]+.
ACHTUNGTRENNUNG
3
=
6.6 Hz, 12H; CH2 CHMe2), 1.19 (d, 3JH,H =6.9 Hz, 12H; C CHMe2),
ꢀ
ꢀ
1.88 (m, 2H; CH2 CHMe2), 2.72 (d, 3JH,H =7.4 Hz, 4H; CH2 CHMe2),
ꢀ
ꢀ
3.29 (sept, 3JH,F =6.9 Hz, 2H; C CHMe2), 3.49 (d, 3JH,F =17.2 Hz, 1H;
ꢀ
NH), 7.13–7.36 ppm (m, 3H; arom. CH); 11B NMR (CDCl3): d=
21.99 ppm; 13C NMR (CDCl3): d=20.13 (CH2 CHMe2), 23.46 (C
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
CHMe2), 26.93 (CH2 CHMe2), 28.43 (C CHMe2), 53.56 (CH2 CHMe2),
122.85 (m-C), 125.17 (p-C), 136.04 (o-C), 145.13 ppm (i-C); 19F NMR
(CDCl3): d=22.75 ppm; MS (EI): m/z (%): 334 [M]+ (18), 291
[MꢀCHMe2]+ (18).
Bruker system: The cell determination was performed with the aid of the
APEX2 program package (Bruker AXS, 2007) followed by integration
with SAINT (Bruker AXS, 2007). SADABS (Bruker AXS, 2006) was
used for the empirical absorption correction.
Di(isopropyl)amino-(N-2,6-tri(isopropyl)anilino)-fluoroborane
(10):
=
IPDS system: The cell determination and integration was done with the
aid of X-AREA (Stoe & Cie, 2002) software.
1
3
Yield 97%; b.p. 1108C (0.01 mbar); H NMR (CDCl3): d=0.92 [d, JH,H
6.7 Hz, 12H; N ACHTUNGTRENNUNG
(CHMe2)2], 1.19 (d, 3JH,H =6.8 Hz, 6H; C CHMe2), 1.22
ꢀ
ꢀ
3
3
3
The data were reduced in XPREP and the structures were solved by
direct methods with SHELXS.[25] The refinement against F2 was done
with SHELXL.[26]
ꢀ
(d, JH,H =6.8 Hz, 6H; C CHMe2), 1.29 (dd, JH,H =6.7, JH,F =1.9 Hz, 6H;
C CHMe2), 3.00 [sept, 3JH,H =6.7 Hz, 2H; N
ACTHNUGTRNEUN(G CHMe2)2], 3.02 (sept,
ꢀ
ꢀ
3JH,H =6.7 Hz, 2H; N CHMe2), 3.30 (sept, 3JH,H =6.8 Hz, 2H;
ꢀ
ꢀ
C
CHMe2), 7.01–7.15 ppm (m, 3H; arom. CH); 13C NMR (CDCl3): d=
CCDC-713642 (6), 713643 (7), 713644 (9), 713645 (10), 713646 (11),
713647 (13) and 713648 (16) contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge from The
request/cif.
22.56 (d, 3JC,F =4.3 Hz; N CHMe2), 22.87 [N
ACHTNUGTRENUNG(CHMe2)2], 23.46 (C
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
CHMe2), 24.64 (C CHMe2), 27.78 (C CHMe2), 44.35 [N ACHTUNTRGNEUNG(CHMe2)2],
ꢀ
55.29 (N CHMe2), 124.26 (m-C), 125.54 (p-C), 142.14 (o-C), 146.94 ppm
(i-C); 11B NMR (CDCl3): d=23.39 ppm; 19F NMR (CDCl3): d=
48.86 ppm; MS (EI): m/z (%): 348 (15) [M]+, 333 (100) [MꢀMe]+.
Di(isopropyl)amino-(N-trimethylsilyl-2,6-di(isopropyl)anilino)-fluorobor-
ane (11): Yield 95%; m.p. 838C; b.p. 808C (0.01 mbar); 1H NMR
ACTHNUTRGNEUNG
(CDCl3): d=0.10 [d, 5JH,F =2.2 Hz, 9H; Si(CH3)3], 0.97 [d, 3JH,H =6.5 Hz,
12H; C CH
(CH3)2], 1.18 [d, 3JH,H =6.8 Hz, 6H; N CH
E
ꢀ
ꢀ
Acknowledgements
3JH,H =6.8 Hz, 6H; N CH
(CH3)2], 2.94 (sept, 3JH,H =6.5 Hz, 2H;
ꢀ
ꢀ
C
CHMe2), 3.41 (sept, 3JH,H =6.8 Hz, 2H; N CHMe2), 6.8–7.07 ppm (m,
ꢀ
We gratefully acknowledge financial support from the Deutsche For-
schungsgesellschaft, the Volkswagen Stiftung, the Fonds der Chemischen
Industrie (H.O.), and CHEMETALL GmbH Frankfurt.
3H; arom. CH); 13C NMR (CDCl3): d=1.75 [Si
N
ꢀ
ꢀ
ꢀ
ꢀ
(CH3)2], 24.19 [N CH
E
(CH3)2], 27.77 [C CHMe2],
44.07 [d, 3JC,F =2.4 Hz, N CHMe2], 123.59 (p-C), 124.99 (m-C), 140.81
(o-C), 145.74 ppm (i-C); 11B NMR (CDCl3): d=22.61 ppm; 19F NMR
(CDCl3): d=53.00 ppm; 29Si NMR (CDCl3): d=8.30 ppm (d, 3JSi,F =9.6);
MS (EI): m/z (%): 378 [M]+ (3), 363 [MꢀMe]+ (100), 335 [MꢀCHMe2]+
(90).
ꢀ
[1] For example, a) U. Flierler, D. Leusser, H. Ott, G. Kehr, G. Erker,
S. Grimme, D. Stalke, Chem. Eur. J. 2009, 15, 4595–4601, preceding
paper; b) K.-A. Østby, G. Gundersen, A. Haaland, H. Nçth, Dalton
Trans. 2005, 2284–2291; c) K.-A. Østby, A. Haaland, G. Gundersen,
H. Nçth, Organometallics 2005, 24, 5318–5328; d) A. Beste, O.
2045; e) V. Jonas, G. Frenking, M. T. Reetz, J. Am. Chem. Soc. 1994,
116, 8141–8753; f) A. Haaland, Angew. Chem. 1985, 97, 1017–1032;
Di
ACHTUNGTRENNUNG(isobutyl)amino-(N-trimethylsilyl-2,6-di(isopropyl)anilino)-fluoro-
borane (12): Yield 88%; b.p. 898C (0.01 mbar); 1H NMR (CDCl3): d=
5
3
ꢀ
0.15 [d, JH,F =2.2 Hz, 9H; Si
ACHTNUGTNERUN(GN CH3)3], 0.71 [d, JH,H =6.7 Hz, 12H; C CH-
(CH3)2], 1.22 [d, 3JH,H =6.9 Hz, 6H; CH2 CH
ACTHUGNNTRE(GUN CH3)2], 1.25 [d, JH,H =
3
ꢀ
6.9 Hz, 6H; CH2 CHACHTUNGTRENNUNG
(CH3)2], 2.43 (d, 3JH,H =6.1 Hz, 4H; CH2CHMe2),
ꢀ
2.92 (sept, 3JH,H =6.7 Hz, 2H; C CHMe2), 3.39 (m, 2H; CH2CHMe2),
ꢀ
7.06–7.13 ppm (m, 3H; arom. CH); 11B NMR (CDCl3): d=21.73 ppm;
13C NMR (CDCl3): d=1.75 [d, 4JC,F =4.5 Hz, Si
(CH3)3], 20.18 [C CH-
ꢀ
399–418; d) H. Nçth, S. Weber, B. Rasthofer, C. Narula, A. Kon-
stantinov, Pure Appl. Chem. 1983, 55, 1453–1461; e) P. Paetzold, A.
ꢀ
A
E
N
CHMe2), 27.81 (CH2CHMe2), 52.56 (d, 3JC,F =4.7 Hz; CH2CHMe2),
123.16 (p-C), 125.25 (m-C), 140.75 (d, 4JC,F =8.4 Hz; o-C), 145.87 ppm (i-
C); 19F NMR (CDCl3): d=46.06 ppm; 29Si NMR (CDCl3): d=8.00 ppm
(d, 3JSi,F =9.5 Hz); MS (EI): m/z (%): 406 [M]+ (6), 391 [MꢀMe]+ (18),
363 [MꢀCHMe2]+ (100).
4608
ꢂ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 4602 – 4609