10.1002/ejic.201900003
European Journal of Inorganic Chemistry
FULL PAPER
added (in this order!). After filtration (celite padded frit/F4), the orange to
red filtrate was concentrated to ca. 5 ml, frozen with liquid nitrogen and
warmed to room temperature to trigger crystallization. Fractional
crystallization at 5 °C yielded two crops of crystals. The crude product was
then recrystallized from CH2Cl2, washed with a minimum amount of n-
hexane and dried in vacuo. Yield: 1.608 g (2.59 mmol, 32.9%). Further
fractions of the crude product yielded a mixture of C-C coupling product 3a
and Mes*N(SiMe3)H as main products (ca. 60%).
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Mp.: 89 °C. CHN calc. (found) in %: C 41.18 (40.74), H 6.25 (6.03), N 2.29
(2.15). 1H NMR (300.0 K, CD2Cl2, 250.13 MHz): 0.44 (s, 2J(1H-29Si) =
6.3 Hz, 9 H, Si(CH3)3), 1.30 (s, 9 H, p-C(CH3)3), 1.54 (s, 18 H, o-C(CH3)3),
7.57 (s, 2 H, arom. CH).
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Synthesis of [Mes*N(SiMe3)BiCl][GaCl4] (2[GaCl4]). To a stirred solution
of Mes*N(SiMe3)BiCl2 (1, 0.613 g, 1.00 mmol) in CH2Cl2 (2 mL) was added
GaCl3 (0.176 g, 1.00 mmol) in CH2Cl2 (1 mL) dropwise at −15 °C. The
resulting deep red solution was stirred for 20 min at this temperature. Upon
concentration to ca. 1 mL, the solution was stored at −80 °C for 12 h
resulting in the deposition of X-ray quality crystals of 2[GaCl4]. The red
solid was washed two times with n-pentane (1 mL) at −60 °C and dried in
vacuo at room temperature for 30 min. Yield: 0.712 g (0.90 mmol, 90.2 %).
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(30.93),
H
4.73 (4.19),
N
1.69 (1.76). 1H NMR (300.0 K, CD2Cl2,
250.13 MHz): 0.56 (s, 9 H, J{1H-29Si) = 6.3 Hz, Si(CH3)3), 1.32 (s, 18 H,
o-C(CH3)3), 1.36 (s, 9 H, p-C(CH3)3), 5.33 (s, 1 H, ½ CH2Cl2) 7.92 (s, 2 H,
arom. CH).
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Synthesis of Mes*N(SiMe3)BiI2 (4). Mes*N(SiMe3)BiCl2 (1, 0.181 g,
0.30 mmol) was dissolved in fluorobenzene (5 mL) and cooled to −20 °C.
To this solution Me3SiI (0.140 g, 0.70 mmol) was added dropwise. The
dark red solution was stirred for 15 min at −20 °C and afterward filtered
(F4). The filtrate was concentrated at −10 °C. Upon storage at −24 °C for
8 h 4 was obtained as red crystals (suitable for single crystal diffraction).
The supernatant was removed by syringe and the remaining solid was
dried in vacuo for 1 h at room temperature. Yield: 0.049 g (0.06 mmol,
20.0%) 4 as a red crystalline solid.
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Mp.: 78 °C. CHN calc. (found) in %: C 31.71 (31.83), H 4.82 (4.92), N 1.76
(1.59). 1H NMR (298.2 K, CD2Cl2, 300.13 MHz): 0.47 (s, 9 H, 2J{1H-29Si} =
6.23 Hz, Si(CH3)3), 1.29 (s, 9 H, p-C(CH3)3), 1.54 (s, 18 H, o-C(CH3)3),
7.55 (s, 2 H, arom. CH).
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Acknowledgments
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We thank the University of Rostock for financial support.
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Keywords: Bismuth • metal--arene interaction • amino-
bismuthanes • C-C coupling •
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