Z. Hao et al. / Journal of Organometallic Chemistry 749 (2014) 350e355
353
3. Conclusions
4.4. Synthesis of 2-(8-(C9H6N)NC(H)C6H4eHN(2,6-Me2C6H3))
(LdH)
Four nickel complexes bearing N,N,N-tridentated quinolinyl
anilido-imine ligands have been synthesized and characterized.
The nickel complexes exhibit square planar coordination around
the metal center. When activated with MAO, these nickel com-
plexes show moderate activities in vinyl-addition polymerization of
norbornene.
To a solution of 2-(2,6-diisopropylphenylamino)benzaldehyde
(2.81 g, 10.0 mmol) in hexane (30 mL), quinolin-8-amine (1.60 g,
11.0 mmol) and few drops of formic acid were added. After
refluxing for 12 h, the hexane was removed under reduced pres-
sure. Treatment of the residue with methanol affords the LdH as
yellow powder. Yield 2.72 g (67%). Anal. Calcd for C28H29N3 (%): C,
82.52; H, 7.17; N, 10.31. Found: C, 82.61; H, 7.20; N, 10.28. 1H NMR
4. Experimental section
(300 MHz, CDCl3, 25 ꢀC):
d
1.16 (d, 3J ¼ 6.0 Hz, 6H, CH(CH3)2), 1.22
4.1. General methods
(d, 3J ¼ 9.0 Hz, 6H, CH(CH3)2), 3.29e3.38 (m, 2H, CH(CH3)2), 6.29
(d, 3J ¼ 9.0 Hz, 1H, AreH), 6.69 (m, 1H, AreH), 7.11e7.16 (m, 2H,
AreH), 7.24e7.27 (m, 3H, AreH), 7.35e7.41 (m, 2H, AreH), 7.44e
7.47 (m, 1H, AreH), 7.55 (t, 3J ¼ 9.0 Hz, 1H, AreH), 7.63e7.65 (m,
1H, AreH), 8.13 (d, 3J ¼ 9.0 Hz, 1H, AreH), 8.84e8.86 (m,
3J ¼ 4.1 Hz, J ¼ 1.6 Hz, 1H, AreH), 8.87 (s, 1H, AreCH]N), 11.02 (s,
All manipulations involving air and moisture-sensitive com-
pounds were carried out under an atmosphere of dried and purified
nitrogen using standard Schlenk or dry box techniques. Toluene
and hexane were dried over sodium/benzophenone and distilled
under nitrogen prior to use. Elemental analyses were performed on
a Varian EL microanalyzer. NMR spectra were recorded on a Varian
Mercury-300 NMR spectrometer at room temperature in CDCl3.
2,6-dimethylaniline and 2,6-diisopropylaniline were purchased
from Aldrich.
1H, AreNH). 13C NMR (75 MHz, CDCl3, 25 ꢀC):
d 23.27 (s, 2C,
ArC(CH3)2), 25.02 (s, 2C, ArC(CH3)2), 28.71 (s, 2C, ArC(CH3)2),
112.36, 115.31, 117.43, 118.26, 121.57, 123.87, 124.89, 126.91, 129.25,
132.23, 134.86, 135.42, 135.87, 142.80, 147.90, 149.38, 150.06,
150.38, 164.76 (s, 1C, CH]N) ppm.
4.2. Synthesis of (2-(2,6-dimethylphenylamino)benzaldehyde)
4.5. Synthesis of [2-(2,6-Me2C6H3NC(H)C6H4eNC9H6N)]NiCl (1a)
2,6-Dimethylaniline (3.00 g, 24.8 mmol), Pd(OAc)2 (43.6 mg,
0.194 mmol), NaOtBu (2.86 g, 29.7 mmol), bis[2-(diphenylphos-
phino)phenyl]ether (DPEphos) (160.5 mg, 0.298 mmol), 1,3-
dioxolane protected 2-bromobenzaldehyde (6.27 g, 27.3 mmol)
and degassed toluene (50 mL) were added into a flask. After stirring
at 100 ꢀC for 10 h, water (40 mL) and toluene (100 mL) were added
and the toluene phase was collected. p-TsOH (2.08 g) was added
and the solution was stirred for 2 h and washed with concentrated
aqueous NaHCO3 (30 mL). The organic solution was dried with
anhydrous MgSO4 and the solvent was removed by rotary evapo-
rator to give a residue which was purified by column chromatog-
raphy on silica gel eluting with ethyl acetate and petroleum ether
(v/v, 1:30). Yield (3.91 g, 70%). Anal. Calcd for C15H15NO (%): C,
79.97; H, 6.71; N, 6.22. Found: C, 79.81; H, 6.67; N, 6.28. 1H NMR
A hexane solution of nBuLi (0.66 mL, 1.05 mmol) was added
dropwise to a THF (20 ml) solution of LaH (0.35 g, 1.00 mmol)
at ꢂ78 ꢀC. The mixture was stirred for 1 h and then NiCl2(DME)
(0.22 g, 1.00 mmol) was added. The reaction mixture was allowed
to warm gradually to room temperature and stirred overnight.
The solvent was removed under reduce pressure and the residue
was treated with toluene, after evaporation of the toluene to
dryness, the product was obtained as purple powder. Yield, 0.37 g
(85%). Anal. Calcd for C24H20ClN3Ni (%): C, 64.84; H, 4.53; N, 9.45.
Found: C, 64.75; H, 4.61; N, 9.60. 1H NMR (300 MHz, CDCl3,
25 ꢀC):
d
2.82 (s, 6H, CH3), 6.69 (t, 3J ¼ 6.0 Hz, 1H, AreH), 7.07 (s,
1H, HC]N), 7.12 (d, 3J ¼ 9.0 Hz, 1H AreH), 7.23e7.30 (m, 5H Are
H), 7.40 (t, 3J ¼ 9.0 Hz, 1H, AreH), 7.67 (d, 3J ¼ 9.0 Hz, 1H, AreH),
7.95 (d, 3J ¼ 9.0 Hz, 1H, AreH), 8.17 (d, 3J ¼ 9.0 Hz, 1H, AreH), 8.67
(d, 3J ¼ 6.0 Hz, 1H, AreH). 13C NMR (75 MHz, CDCl3, 25 ꢀC):
(300 MHz, CDCl3, 25 ꢀC):
d
2.19 (s, 6H, CH3), 6.21 (d, 3J ¼ 8.4 Hz, 1H,
AreH), 6.76 (m, 1H, AreH), 7.16 (s, 3H, AreH), 7.29e7.22 (m, 1H, Are
d
20.03 (s, 2C, ArCH3), 116.45, 116.94, 117.41, 118.03, 121.47, 126.13,
H), 7.56 (dd, 3J ¼ 7.8 Hz, J ¼ 1.6 Hz, 1H, AreH), 9.55 (s, 1H, AreCHO),
128.01, 128.23, 133.68, 134.07, 138.66, 151.36, 164.37 (s, 1C, CH]N)
ppm.
9.96 (s, 1H, AreNH). 13C NMR (75 MHz, CDCl3, 25 ꢀC):
d 18.3 (s, 2C,
ArCH3), 116.0, 118.4, 112.3, 127.0, 128.6, 135.8, 136.4, 136.7, 149.6,
194.3 (s, 1C, CH]N) ppm.
4.6. Synthesis of [2-(2,6-iPr2C6H3NC(H)C6H4eNC9H6N)]NiCl (1b)
4.3. Synthesis of 2-(8-(C9H6N)NC(H)C6H4eHN(2,6-Me2C6H3))
(LcH)
Complex 1b was synthesized in the same procedure as that for
1a with LbH (0.41 g, 1.00 mmol) and NiCl2(DME) (0.22 g,
1.00 mmol) as starting materials or reagents. Pure 1b was obtained
as purple powder. Yield: 0.44 g (88%). Single crystals for X-ray
diffraction analysis were obtained from hexane/THF mixed solu-
tion. Anal. Calcd for C28H28ClN3Ni (%): C, 67.17; H, 5.64; N, 8.39.
Found: C, 67.25; H, 5.60; N, 8.48. 1H NMR (300 MHz, CDCl3, 25 ꢀC):
To a solution of 2-(2,6-dimethylphenylamino)benzaldehyde
(2.25 g, 10.0 mmol) in hexane (30 mL) quinolin-8-amine (1.6 g,
11.0 mmol) and few drops of formic acid were added. After
refluxing for 12 h, the resulted mixture was evaporated to dryness.
Treatment of the residue with methanol affords the LcH as yellow
powder. Yield 2.28 g (65%). Anal. Calcd for C24H21N3 (%): C, 82.02; H,
6.02; N, 11.96. Found: C, 82.12; H, 6.07; N, 11.91. 1H NMR (300 MHz,
d
1.17 (d, JHeH ¼ 6.0 Hz, 6H, CH(CH3)2), 1.59 (d, 3J ¼ 6.0 Hz, 6H,
CH(CH3)2), 4.27 (sept, 3J
¼
6.0 Hz, 2H, CH(CH3)2), 6.69 (t,
CDCl3, 25 ꢀC):
d
2.36 (s, 6H, CH3), 6.33 (d, 3J ¼ 6.0 Hz,1H, AreH), 6.72
3J ¼ 6.0 Hz, 1H, AreH), 7.11 (s, 1H, HC]N), 7.12 (d, 3J ¼ 9.0 Hz, 1H
AreH), 7.23e7.30 (m, 5H AreH), 7.41 (t, 3J ¼ 9.0 Hz, 1H, AreH),
7.69 (d, 3J ¼ 9.0 Hz, 1H, AreH), 7.96 (d, 3J ¼ 9.0 Hz, 1H, AreH), 8.16
(d, 3J ¼ 9.0 Hz, 1H, AreH), 8.69 (d, 3J ¼ 6.0 Hz, 1H, AreH). 13C NMR
(m, 1H, AreH), 7.07e7.20 (m, 4H, AreH), 7.37e7.41 (m, 2H, AreH),
7.45e7.48 (m, 1H, AreH), 7.54 (t, 3J ¼ 9.0 Hz, 1H, AreH), 7.62e7.65
(m,1H, AreH), 8.13 (dd, 3J ¼ 9.0 Hz, J ¼ 1.7 Hz,1H, AreH), 8.86 (s,1H,
AreCH]N), 8.88 (dd, 3J ¼ 4.1 Hz, J ¼ 1.6 Hz, 1H, AreH), 11.10 (s, 1H,
(75 MHz, CDCl3, 25 ꢀC):
d 23.89 (s, 2C, ArCH(CH3)2), 24.79 (s, 2C,
AreNH). 13C NMR (75 MHz, CDCl3, 25 ꢀC):
d
18.77 (s, 2C, ArCH3),
ArCH(CH3)2), 29.31 (s, 2C, ArCH(CH3)2), 116.41, 116.91, 117.43,
117.08, 121.47, 123.37, 123.91, 126.84, 128.18, 129.17, 133.63, 134.11,
138.58, 141.51, 145.58, 148.07, 149.32, 149.38, 151.51, 164.32 (s, 1C,
CH]N) ppm.
112.17, 115.64, 117.88, 118.17, 121.59, 125.00, 126.17, 128.45, 129.24,
132.36, 134.97, 135.92, 136.78, 138.25, 142.85, 148.62, 149.19, 150.08,
164.57 (s, 1C, CH]N) ppm.