X. Wang et al. / Journal of Organometallic Chemistry 690 (2005) 2934–2940
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2. Experimental
2.2.3. Ni[3-methyl-1-picolyimidazolium]Cl2.5I0.5 (3)
A stirred DMSO solution (5.0 mL) of 3-methyl-1-pic-
olylimidazolium iodide (301 mg, 1 mmol) and anhy-
drous NiCl2 (130 mg, 1 mmol) was heated to 140 ꢁC
for 2 days, during which time the reaction solution
had bleached to green. The remaining DMSO was then
removed in vacuo at 50 ꢁC to give a green solid, which
was re-crystallized with MeOH/Et2O to give green crys-
2.1. General procedures
All manipulations were performed using standard
Schlenk techniques under an atmosphere of argon.
Methanol was dried over Mg, CH2Cl2 over CaH2,
and then distilled under nitrogen immediately prior to
use. Methylaluminoxane (MAO), 1-methylimidazole
and 2-picolychloride hydrochloride were purchased
from Witco and Acros, respectively. Other solvents
were used as received as technical grade solvents.
1-Benzylimidazol were prepared according to the liter-
atures [22]. 1H NMR and 13C NMR spectra were
recorded on a VAVCE-DMX 500 Spectrometer in
CDCl3, MeOH-d, DMSO-d. 13C NMR spectra of poly-
ethylene were obtained using o-dichlorobenzene as a
solvent on FX-100 NMR spectrometer at 130 ꢁC. Ele-
mental ananlysis was performed on Elementar III vario
EI Analyzer.
1
tals. Yield: 0.292 g (76%). H NMR (500 Hz, DMSO-d,
ppm): d 9.33 (s, 1H, NC(H)N), 8.64 (s, 1H, C5H4N),
7.91 (m, 1H, C5H4N), 7.80 (s, 1H, HCCH), 7.75 (s,
1H, HCCH), 7.55 (m, 1H, C5H4N), 7.40 (s, 1H,
C5H4N), 5.58 (s, 2H, NCH2), 3.90 (s, 3H, NCH3). Anal.
Calc. for C10H12Cl2.5I0.5N3Ni: C, 31.18; H, 3.12; N,
10.91. Found: C, 31.43; H, 3.50; N, 10.42%.
2.2.4. Ni[3-benzyl-1-picolyimidazolium]Cl2.5I0.5 (4)
This complex was prepared in a manner analogous to
that described above, using 2 (377 mg, 1 mmol) and
NiCl2 (130 mg, 1 mmol) in 5 mL of DMSO, and then
re-crystallized with MeOH/Et2O to yield green crystals.
Yield: 0.368 g (80%). 1H NMR (500 Hz, DMSO-d,
ppm): d 9.52 (s, 1H, NC(H)N), 8.60 (s, 1H, C5H4N),
7.91 (m, 1H, C5H4N), 7.86 (m, 1H, HCCH), 7.83
(s,1H, HCCH), 7.54 (m, 1H, C5H4N), 7.44 (m, 1H,
C5H4N), 7.43 (m, 5H, Ph), 5.60 (s, 2H, CH2Ph), 5.50
2.2. Synthesis
2.2.1. Synthesis of 3-methyl-1-picolyimidazolium iodide
(1)
To
a solution of picolyl chloride (5.85 mmol,
prepared by basifying 0.96 g of picolyl chloride hydro-
chloride) in 20 mL of acetone were added 1-methylim-
idazole (0.470 mL, 5.89 mmol) and NaI (0.88 g,
5.9 mmol). After it was stirred for 48 h, the solution
was filtered through Celite and the solvent was
removed in vacuum to afford a thick brown syrup.
The syrup was re-dissolved in 15 mL of CH2Cl2 and
the solution was filtered to remove residual NaCl.
Addition of 25 mL ether caused an oil to separate
out. The solvent was decanted off, and then the
resulted oil was taken up in 8 mL of CH2Cl2, and
20 mL of ether was added to precipitate the product.
The oily solid that formed was triturated for 2 h and
the resultant powder washed with 10 mL of ether.
Yield: 1.22 g (69%). 1H NMR (500 MHz, DMSO-d,
ppm): d 10.31 (s, 1H, NC(H)N), 8.56 (s, 1H, pyridyl),
7.83 (m, 2H, pyridyl), 7.62 (s, 1H, HCCH), 7.32 (s,
1H, HCCH), 7.26 (m, 1H, pyridyl), 5.74 (s, 1H,
NCH2), 4.07 (s, 3H, NCH3).
(s,2H, NCH2). Anal. Calc. for C16H16Cl2.5I0.5N3Ni: C,
41.66; H, 3.47; N, 9.11. Found: C, 42.42; H, 3.59; N,
8.86%.
2.2.5. Co[3-methyl-1-picolyimidazolium]Cl3 (5)
This complex was prepared in a manner analogous to
that described above, using 1 (300 mg, 1 mmol) and
CoCl2 (130 mg, 1 mmol) in 5 mL of DMSO, and then
recrystallized with MeOH/Et2O to yield blue crystals.
Yield: 0.244 g (72%). 1H NMR(500 Hz, MeOH-d,
ppm): d 9.20 (s, 1H, NC(H)N), 8.54 (d, 1H, C5H4N),
7.88 (m, 1H, C5H4N), 7.65 (d, 1H, HCCH), 7.50 (d,
1H, HCCH), 7.43 (m, 2H, C5H4N), 5.56 (s, 2H,
NCH2), 3.45 (s, 3H, NCH3). 13C NMR (500 MHz,
MeOH-d): d 152.9 (pyridyl, C2), 148.9 (pyridyl, C6),
137.3 (pyridyl, C4), 128.5(NCN), 124.6 (pyridyl, C3),
124.0 (pyridyl, C5), 123.4 (NCCN), 122.7 (NCCN),
54.2 (NCH2), 35.3 (NCH3). Anal. Calc. for
C10H12Cl3N3Co: C, 35.35; H, 3.53; N, 12.37. Found:
C, 35.78; H, 3.22; N, 12.65%.
2.2.2. Synthesis of 3-benzyl-1-picolyimidazolium iodide
(2)
2.3. X-ray crystallography
Analogous to the synthesis of 2 but using picolyl
chloride (5.85 mmol), 1-benzylimidazole (0.925 g,
5.85 mmol) and NaI (0.88 g, 5.9 mmol) in 20 mL of ace-
tone, give 2 as a red solid. Yield: 1.32 g (60%). 1H NMR
(500 MHz, CDCl3, ppm): d 10.32 (s, 1H, NC(H)N), 8.56
(m, 1H, pyridyl), 7.80 (d, 2H, HCCH), 7.66 (d, 1H, pyr-
idyl), 7.43 (m, 7H, pyridyl, Ph), 5.74 (s, 2H, CH2Ph),
5.57 (s, 2H, NCH2).
Suitable crystals for X-ray analysis of 2, 4 and 5 were
obtained by slow diffusion of diethyl ether into metha-
nol solutions of the corresponding compound, respec-
tively. X-ray intensity data were collected on the
CCD-Bruker SMART APEX system. The determina-
tion of the unit cell and the collection of intensity data
were performed with graphite-monochromated Mo Ka