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W. Streciwilk et al. / Journal of Organometallic Chemistry 749 (2014) 88e99
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2.3.7. 1,3-Di(p-methylbenzyl)-4,5-di(p-chlorophenyl)-imidazolium
bromide (3g)
Micro analysis calculated for C31 H21Cl2N4Br (600.34 g/mol):
calcd.: C, 62.02; H, 3.53; N, 9.33%; found: C, 61.75; H, 3.01; N, 8.84%.
Melting point: 183e185 ꢁC.
Yield: 53% (0.944 mmol, 546 mg).
1H NMR (
d
ppm, CDCl3, 300 MHz): 10.81 (s, 1H, NCHN), 7.25
7.4 Hz, 4H, CHmethylbenzyl), 7.13e6.88 (m, 12H,
CHmethylbenzyl þ CHchlorophenyl) 5.40 (s, 4H, CH2), 2.23 (s, 6H, CH3).
13C NMR (
ppm, CDCl3, 101 MHz): 138.0 (NCN), 135.6, 132.8,
(d,
J
¼
2.4. General procedure for the synthesis of the 1,3-di(p-substituted
benzyl)-4,5-di(p-substituted phenyl)-imidazol-2-ylidene silver(I)
acetate complexes 4aej and 5c
d
131.8, 131.7, 129.0, 128.3, 127.2, 126.8, 125.9 (Cchlorophenyl
þ
Cmethylbenzyl þ Cimidazole), 53.6 (CH2benzyl), 21.1 (CH3benzyl).
100 mg of the appropriately p-benzyl substituted imidazolium
halide precursor and 2.1 equivalents of silver(I) acetate were dis-
solved in 30 mL of dichloromethane and stirred in darkness at RT
for 3 d (4b), 4 d (4a, 4g, 4j), 5 d (4e, 5c), 6 d (4d), 7 d (4f, 4c) and 8 d
(4i). After filtering off the AgeBr by-product, the solvent was
reduced to approximately 3 mL and by dropwise addition of 5 mL of
pentane, a white powder precipitated. The solvent was decanted
and the white precipitate was washed with pentane (2 ꢃ 10 mL) to
yield the final product as white solid.
IR absorptions (KBr, cmꢂ1): 3421 (m), 3010 (s), 2941 (s), 1619 (s),
1558 (s), 1502 (s), 1452 (s), 817 (s).
MS (m/z, QMSeMS/MS): 498.46 [Mþ ꢂ Br].
Micro analysis calculated for C31H21Cl2N4Br (600.33 g/mol):
calcd.: C, 62.00%; H, 3.53%; N, 9.34%; found: C, 62.75%; H, 3.38%; N,
9.67%.
Melting point: 231e233 ꢁC.
2.3.8. 1,3-Di(p-methoxybenzyl)-4,5-di(p-chlorophenyl)-
imidazolium chloride (3h)
2.4.1. 1,3-Di(benzyl)-4,5-di(p-isopropylphenyl)-imidazole-2-ylidene
silver(I) acetate (4a)
Yield: 52% (0.892 mmol, 508 mg).
1H NMR (
d
ppm, CDCl3, 300 MHz): 11.41 (s, 1H, NCHN), 7.34 (d,
Yield: 65% (0.11 mmol, 75 mg).
J ¼ 8.2 Hz, 4H, CHmethoxybenzyl), 7.06 (dd, J ¼ 11.1 and 8.3 Hz, 8H,
CHchlorophenyl), 6.78 (d, J ¼ 8.2 Hz, 4H, CHmethoxybenzyl), 5.42 (s, 4H,
CH2benzyl), 3.76 (s, 6H, CH3methoxy).
1H NMR (
d
ppm, CDCl3, 300 MHz): 7.23 (d, J ¼ 2.4 Hz, 4H), 7.12e
7.07 (m, 6Hbenzyl pos: 3,4,5), 6.98 (dd, J ¼ 6.8, 3.0 Hz, 4H), 6.94 (d,
J ¼ 8.2 Hz, 4H), 5.31 (s, 4HCH2benzyl), 2.87 (p, J ¼ 6.9 Hz, 2HCHisopropyl),
2.10 (s,CH3acetate), 1.22 (d, J ¼ 6. Hz, 12HCH3isopropyl).
13C NMR (
d ppm, CDCl3, 101 MHz): 160.0 (NCHN), 137.1, 132.0,
131.2, 130.0, 129.5, 127.8, 125.1, 123.0, 114.4 (Cchlorophenyl
þ
13C NMR (
d ppm, CDCl3, 101 MHz): 178.7 (Cacetate), 149.9
Cmethoxybenzyl þ Cimidazole), 55.3 (CH2benzyl), 51.2 (OCH3benzyl).
(NCN), 136.3, 134.1, 132.4, 130.7, 128.8, 128.5, 127.4, 126.5,
125.1 (Cphenyl þ Cbenzyl), 53.6 (CH2benzyl), 33.9 (CHisopropyl), 23.7
(CH3isopropyl), 23.7 (CH3acetate).
IR absorptions (KBr, cmꢂ1): 3421 (m), 3088e2956 (m), 1613 (s),
1514 (s), 1452 (s), 1250 (s), 1178 (s), 821 (s).
MS (m/z, QMSeMS/MS): 530.46 [Mþ ꢂ Cl].
IR absorptions (KBr, cmꢂ1): 3420 (m), 2958 (s), 1577 (s), 1497
(w), 1401 (m), 1339 (w), 825 (s).
Micro analysis calculated for C31H27Cl3N2O2 (565.92 g/mol): C,
65.79; H, 4.81; N, 4.95%; found: C, 64.99; H, 4.54%; N, 4.21%.
Melting point: 129e130 ꢁC.
MS (m/z, QMSeMS/MS): 485.07 [Mþ ꢂ AgOAc].
Micro analysis calculated for C37H39AgN2O2 (651.59 g/mol): C,
68.58; H, 6.18; N, 4.39%. Found: C, 68.08; H, 6.16; N, 4.29%.
Melting point: 132e134 ꢁC.
2.3.9. 1,3-Di(p-methoxycarbonylbenzyl)-4,5-di(p-chlorophenyl)-
imidazolium bromide (3i)
Yield: 60% (1.03 mmol, 687 mg).
2.4.2. 1,3-Di(p-methylbenzyl)-4,5-di(p-isopropylphenyl)-
imidazole-2-ylidene silver(I) acetate (4b)
Yield: 66% (0.11 mmol, 75 mg).
1H NMR (
d ppm, CDCl3, 300 MHz): 11.33 (s, 1H, NCHN), 7.94
(d, J ¼ 8.3 Hz, 4H, CHmethoxycarbonylbenzyl), 7.34e7.19 (m, 8H,
CHchlorophenyl), 7.06 (d, J ¼ 8.3 Hz, 4H, CHmethoxycarbonylbenzyl), 5.62 (s,
4H, CH2benzyl), 3.91 (s, 6H, CH3methoxycarbonyl).
1H NMR (
d
ppm, CDCl3, 300 MHz): 7.11 (d, J ¼ 8.1 Hz, 4H), 7.02 (d,
J ¼ 7.6 Hz, 4H), 6.98e6.92 (d, J ¼ 7.5 Hz, 4H), 6.87 (d, J ¼ 8.0 Hz, 4H),
5.25 (s, 4HCH2benzyl), 2.93e2.82 (m, 2HCHisopropyl), 2.30 (s,
6HCH3benzyl), 2.10 (s, 3HCH3acetate), 1.23 (d, J ¼ 6.9 Hz, 12HCH3isopropyl).
13C NMR (
d ppm, CDCl3, 101 MHz): 166.1 (C]O), 137.4 (NCN),
132.0, 131.6, 130.8, 130.3, 129.6, 129.1, 128.2, 127.9, 122.5
(Cchlorophenyl þ Cmethoxycarbonylbenzyl þ Cimidazole), 52.3 (CH2benzyl),
51.4 (CH3methoxyczrbonlyl).
13C NMR (
d ppm, CDCl3, 101 MHz): 178.5 (Cacetate), 149.8 (NCN),
137.5, 133.4, 132.3, 130.5, 130.6, 129.2, 127.43, 126.5,
125.3 (Cphenyl þ Cbenzyl), 53.3 (CH2benzyl), 33.8 (CHisopropyl), 23.7
(CH3isopropyl), 22.8 (CH3acetate), 21.1 (CH3benzyl).
IR absorptions (KBr, cmꢂ1): 3423 (m), 2950 (s), 1722 (s), 1614 (s),
1434 (s), 1280 (s).
MS (m/z, QMSeMS/MS): 586.48 [Mþ ꢂ Br].
Micro analysis calculated for C33H27BrCl2N2O2 (666.39 g/mol):
C, 59.48%; H, 4.08%; N, 4.20%; found: C, 59.41%; H, 3.87%; N,
3.94%.
IR absorptions (KBr, cmꢂ1): 3024 (w), 2924 (s), 1700 (w), 1576
(s), 1517 (m), 1446 (m), 834 (s).
MS (m/z, QMSeMS/MS): 512 [Mþ ꢂ AgOAc].
Micro analysis calculated for C39H43AgN2O2 (679.64 g/mol): C,
68.92; H, 6.38; N, 4.12%. Found: C, 67.92; H, 6.21; N, 3.62%.
Melting point: 180e182 ꢁC.
Melting point: 128e130 ꢁC.
2.3.10. 1,3-Di(p-cyanobenzyl)-4,5-di(p-chlorophenyl)-imidazolium
bromide (3j)
2.4.3. 1,3-Di(p-methoxybenzyl)-4,5-di(p-isopropylphenyl)-imidazole-
2-ylidene silver(I) acetate (4c)
Yield: 58% (1.01 mmol, 609 mg).
1H NMR (
d
ppm, CDCl3, 300 MHz): 11.51 (s, 1H, NCHN), 7.56 (d,
Yield: (0.092 mmol, 65 mg).
J ¼ 8.2 Hz, 4H, CHcyanobenzyl), 7.42e7.31 (m, 8H, CHchlorophenyl), 7.05
1H NMR (
d
ppm, CDCl3, 300 MHz): 7.12 (d, J ¼ 8.0 Hz, 4H), 6.98e
(d, J ¼ 8.3 Hz, 4H, CHcyanobenzyl), 5.66 (s, 4H, CH2benzyl).
6.87 (m, 4H), 6.77e6.70 (m, 4H), 5.23 (s, 4HCH2isopropyl), 3.78 (s,
6HCH3methoxy), 2.93e2.83 (m, 2HChisopropyl), 2.13 (s, 3HCH3acetate),
1.23 (d, J ¼ 6.9 Hz, 12HCH3isopropyl).
13C NMR (
d ppm, 101 MHz): 140.3 (CN), 136.5 (NCN), 132.7, 132.1,
131.5, 129.5, 128.7, 128.0, 124.9, 123.4, 122.6 (Cphenyl þ Cbenzyl
imidazole), 53.4 (CH2benzyl).
IR absorptions (KBr, cmꢂ1): 3461 (m), 2966 (m), 2224 (s), 1612
þ
C
13C NMR (
d ppm, CDCl3, 101 MHz): 159.2 (NCN), 149.8, 132.2,
130.6, 129.0, 128.4, 126.5, 125.3, 114.1, 113.9 (Cphenyl þ Cbenzyl),
55.2 (OCH3benzyl), 53.1 (CH2benzyl), 33.8, 30.9 (CHisopropyl), 23.8
(CH3isopropyl), 23.7 (CH3acetate).
(s), 1567 (s), 1448 (s), 824 (s).
MS (m/z, QMSeMS/MS): 520.43 [Mþ ꢂ Br].