M. Shu, R. Walz, B. Wu, J. Seebacher, H. Vahrenkamp
7.31 (m, 3 H, Ph), 7.44 (d, J ϭ 8.3 Hz, 4 H, C6H4), 7.72 (d, J ϭ (764.60): calcd. C 56.55, H 5.27, N 10.99, S 12.58; found C 56.31,
FULL PAPER
7.0 Hz, 2 H, Ph) ppm. IR (KBr): ν˜ ϭ 2486 m (BH) cmϪ1
.
H 5.60, N 11.02, S 12.25. 1H NMR (CDCl3): δ ϭ 1.26 [d, J ϭ
7.0 Hz, 12 H, Me (iPr)], 2.93 [sept, J ϭ 7.0 Hz, 2 H, CH (iPr)],
6.38 [s, 1 H, H (pz)], 7.01 [d, J ϭ 2.0 Hz, 2 H, H (im)], 7.07 [d, J ϭ
2.0 Hz, 2 H, H (im)], 7.28 (m, 8 H, Ar), 7.45 (m, 3 H, Ar), 7.62 (d,
L8: By procedure B from KBH4 (0.70 g, 13.0 mmol), the pyrazole
(2.26 g, 14.3 mmol) and the imidazole (5.35 g, 26.0 mmol). Yield
6.79 g (85%); m.p. 185 °C (dec.). C30H28BKN6O2S2 (618.63): calcd.
C 58.25, H 4.56, N 13.58, S 10.37; found C 57.99, H 4.60, N 13.54,
J ϭ 7.4 Hz, 2 H, Ph) ppm. IR (KBr): ν˜ ϭ 2512 w (BH) cmϪ1
.
1
1f: From L8 (301 mg, 0.49 mmol) and ZnI2 (155 mg, 0.49 mmol).
Yield 257 mg (69%), m.p. 230 °C (dec.). C30H28BIN6-
O2S2Zn·0.5(CH2Cl2) (771.83 ϩ42.47): calcd. C 44.99, H 3.59, N
10.32, S 7.88; found C 45.79, H 3.95, N 10.75, S 8.25. 1H NMR
(CDCl3): δ ϭ 2.49 [s, 3 H, Me (pz)], 3.85 (s, 6 H, OMe), 5.32 (s, 1
H, CH2Cl2), 6.15 [s, 1 H, H (pz)], 6.91Ϫ7.95 [m, 15 H, H (im) ϩ
S 10.43. H NMR ([D6]DMSO): δ ϭ 2.43 [s, 3 H, Me (pz)], 3.73
(s, 6 H, OMe), 6.24 [s, 1 H, H (pz)], 6.76 [d, J ϭ 2.1 Hz, 2 H, H
(im)], 6.82 [d, J ϭ 2.1 Hz, 2 H, H (im)], 6.85Ϫ7.49 (m, 1 H, Ar),
7.74 (d, J ϭ 7.1 Hz, 2 H, Ph) ppm. IR (KBr): ν˜ ϭ 2441 w (BH)
cmϪ1
.
L9: By procedure A from (0.54 g, 10.0 mmol) of KBH4, (3.00 g,
20.0 mmol) of the pyrazole and (6.24 g, 40.0 mmol) of the imidaz-
ole. Yield 0.51 g (10%), m.p. 160 °C (dec.). The product contained
considerable amounts of impurities. 1H NMR ([D6]DMSO): δ ϭ
1.18 [s, 9 H, tBu (pz)], 1.73 [s, 18 H, tBu (im)], 2.15 [s, 3 H, Me
(pz)], 5.59 [s, 1 H, H (pz)], 6.26 [d, J ϭ 2.0 Hz, 2 H, H (im)], 6.79
Ar] ppm. IR (KBr): ν˜ ϭ 2511 w (BH) cmϪ1
.
Zinc Nitrate Complexes
2a: A solution of L3 (196 mg, 0.33 mmol) in 5 mL of dichlorometh-
ane was added dropwise with stirring to solution of
a
[d, J ϭ 2.0 Hz, 2 H, H (im)] ppm. IR (KBr): ν˜ ϭ 2496m (BH) cmϪ1
.
Zn(NO3)2·6H2O (95 mg, 0.34 mmol) in 10 mL of methanol. After
4 h of stirring, the precipitate was filtered off. Recrystallisation
from dichloromethane/acetonitrile yielded 158 mg (71%) of 2a,
m.p. 220 °C (dec.). C30H28BN7O3S2Zn (674.93): calcd. C 53.39, H
Zinc Halide Complexes. General Procedure: A solution of the zinc
halide in 10 mL of methanol was added dropwise, with stirring, to
a solution of the ligand in 50 mL of dichloromethane. After 2 h of
stirring, the solution was filtered, the filtrate reduced to half of its
volume in vacuo and then cooled to Ϫ30 °C overnight. The re-
sulting precipitate of the raw product was filtered off, washed with
1Ϫ2 mL of methanol and dried in vacuo. If necessary it was recrys-
tallised from CH2Cl2/CH3OH or CH2Cl2/CH3CN. All L·ZnHal
complexes were obtained as colourless powders.
1
4.18, N 14.53, S 9.50; found C 53.29, H 4.29, N 14.42, S 9.30. H
NMR (CD2Cl2): δ ϭ 1.96 [s, 3 H, Me1 (tol)], 2.25 [s, 3 H, Me2
(tol)], 2.53 [s, 3 H, Me (pz)], 6.46 [s, 1 H, H (pz)], 6.96 [d, J ϭ
2.2 Hz, 2 H, H (im)], 7.08 [d, J ϭ 2.2 Hz, 2 H, H (im)], 7.37 (m,
11 H, Ar), 7.52 (d, J ϭ 6.0 Hz, 2 H, Ph) ppm. IR (KBr): ν˜ ϭ 2479
w (BH), 1382 vs (NO3), 1294 vs (NO3) cmϪ1
.
2b: Like 2a from L6 (214 mg, 0.33 mmol) and Zn(NO3)2·6H2O
(95 mg, 0.34 mmol). Yield 169 mg (73%); m.p. 180 °C (dec.).
C34H36BN7O3S2Zn (731.04): calcd. C 55.86, H 4.96, N 13.41, S
1a: From L1 (200 mg, 0.46 mmol) and ZnCl2 (63 mg, 0.46 mmol).
Yield 57 mg (25%); m.p. 225 °C (dec.). C18H20BClN6S2Zn (496.20):
calcd. C 43.57, H 4.06, N 16.94; found C 42.86, H 4.13, N 16.32.
1H NMR (CDCl3): δ ϭ 2.42 [s, 3 H, Me (pz)], 3.57 [s, 6 H, Me
(im)], 6.22 [s, 1 H, H (pz)], 6.60 [d, J ϭ 2.0 Hz, 2 H, H (im)], 7.15
[d, J ϭ 2.0 Hz, 2 H, H (im)], 7.28 (m, 3 H, Ph), 7.74 (d, J ϭ 7.4 Hz,
1
8.77; found C 56.26, H 5.46, N 12.87, S 8.01. H NMR (CDCl3):
δ ϭ 1.27 [d, J ϭ 6.9 Hz, 12 H, Me (iPr)], 2.96 [sept, J ϭ 6.9 Hz, 2
H, CH (iPr)], 6.40 [s, 1 H, H (pz)], 7.00 [s, 4 H, H (im)], 7.36 (s, 8
H, Cum), 7.38 (m, 3 H, Ph), 7.56 (d, J ϭ 5.4 Hz, 2 H, Ph) ppm.
2 H, Ph) ppm. IR (KBr): ν˜ ϭ 2503 m (BH) cmϪ1
.
IR (KBr): ν˜ ϭ 2486 w (BH), 1373 s (NO3), 1292 s (NO3) cmϪ1
.
1b: From L2 (300 mg, 0.52 mmol) and ZnCl2 (71 mg, 0.52 mmol).
Yield 156 mg (48%); m.p. 215 °C (dec.). C28H24BClN6S2Zn
(620.33): calcd. C 54.21, H 3.90, N 13.55; found C 54.68, H 4.05,
2c: Like 2a from L8 (307 mg, 0.52 mmol) and Zn(NO3)2·4H2O
(137 mg, 0.52 mmol). Yield 115 mg (31%), m.p. 215 °C (dec.).
C30H28BN7O5S2Zn (706.93): calcd. C 50.97, H 3.99, N 13.87, S
1
N 13.57. H NMR (CDCl3): δ ϭ 2.29 [s, 3 H, Me (pz)], 6.29 [s, 1
1
9.07; found C 50.43, H 4.28, N 13.51, S 8.93. H NMR (CDCl3):
H, H (pz)], 6.75 [d, J ϭ 2.4 Hz, 2 H, H (im)], 6.81 [d, J ϭ 2.4 Hz,
2 H, H (im)], 7.30Ϫ7.51 (m, 13 H, Ar), 7.53 (d, J ϭ 7.4 Hz, 2 H,
δ ϭ 2.44 [s, 3 H, Me (pz)], 3.75 (s, 6 H, OMe), 6.32 [s, 1 H, H (pz)],
6.86 [d, J ϭ 2.2 Hz, 2 H, H (im)], 6.96 [d, J ϭ 2.2 Hz, 2 H, H (im)],
7.10Ϫ7.48 (m, 11 H, Ar), 7.54Ϫ7.60 (m, 2 H, Ph) ppm. IR (KBr):
Ph) ppm. IR (KBr): ν˜ ϭ 2507 m (BH) cmϪ1
.
ν˜ ϭ 2489 w (BH), 1384 vs (NO3), 1294 vs (NO3) cmϪ1
.
1c: From L3 (196 mg, 0.33 mmol) and ZnCl2 (46 mg, 0.34 mmol).
Yield 180 mg (84%); m.p. 270 °C (dec.). C30H28BClN6S2Zn
(648.38): calcd. C 55.57, H 4.35, N 12.96, S 9.89; found C 55.23,
ZnL2 Complexes
1
H 4.58, N 13.33, S 9.34. H NMR (CDCl3): δ ϭ 2.06 [s, 3 H, Me1
3a: A solution of (171 mg, 0.46 mmol) of Zn(ClO4)2·6H2O in
20 mL of methanol was added with stirring to a solution of
(200 mg, 0.46 mmol) of L1 in 50 mL of dichloromethane. After
30 min, powdered KOH (29 mg, 0.50 mmol) was added. After 20 h
of stirring and filtration, the volume of the solution was reduced
to one half in vacuo. Cooling to Ϫ4 °C overnight produced a
colourless precipitate of 6a (characterisation see below). Attempts
to purify this product by dissolution in dichloromethane and slow
concentration yielded, after 4 weeks, 18 mg (4%) of colourless crys-
talline 3a; m.p. 230 °C (dec.). C36H40B2N12S4Zn·3H2O (856.14
ϩ54.02): calcd. C 47.51, H 5.09, N 18.47; found C 46.40, H 5.03,
(tol)], 2.28 [s, 3 H, Me2 (tol)], 2.49 [s, 3 H, Me (pz)], 6.39 [s, 1 H,
H (pz)], 6.88 [s, 2 H, H (im)], 7.05 [s, 2 H, H (im)], 7.25Ϫ7.37 (m,
11 H, Ar), 7.53 (d, J ϭ 7.2 Hz, 2 H, Ph) ppm. IR (KBr): ν˜ ϭ 2559
w (BH) cmϪ1
.
1d: From L5 (614 mg, 1.00 mmol) and ZnCl2 (136 mg, 1.00 mmol).
Yield 0.25 mg (37%), m.p. 220 °C (dec.). C32H32BClN6S2Zn
(676.43): calcd. C 56.82, H 4.77, N 12.42; found C 56.99, H 4.70,
1
N 12.36. H NMR (CDCl3): δ ϭ 2.14 [s, 6 H, Me (xyl)], 2.37 [s, 6
H, Me (xyl)], 2.48 [s, 3 H, Me (pz)], 6.38 [s, 1 H, H (pz)], 6.83 [d,
J ϭ 2.0 Hz, 2 H, H (im)], 6.99 [d, J ϭ 2.0 Hz, 2 H, H (im)],
7.00Ϫ7.17 (m, 6 H, xyl), 7.31Ϫ7.37 (m, 3 H, Ph), 7.53Ϫ7.58 (m, 2
1
N 19.25. H NMR (CDCl3): δ ϭ 1.49 (s, 6 H, H2O), 2.38 [s, 6 H,
Me (pz)], 3.43 [s, 12 H, Me (im)], 6.22 [s, 2 H, H (pz)], 6.67 [d, J ϭ
2.0 Hz, 4 H, H (im)], 7.17 [d, J ϭ 2.0 Hz, 4 H, H (im)], 7.31 (m, 6
H, Ph), 7.75 (d, J ϭ 7.4 Hz, 4 H, Ph) ppm. IR (KBr): ν˜ ϭ 2500 m
H, Ph) ppm. IR (KBr): ν˜ ϭ 2505 m (BH) cmϪ1
.
1e: From L6 (206 mg, 0.33 mmol) and ZnCl2 (46 mg, 0.34 mmol).
Yield 169 mg (67%), m.p. 240 °C (dec.). C36H40BClN6S3Zn
(BH) cmϪ1
.
2508
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2003, 2502Ϫ2511