V.O. Nyamori et al. / Journal of Organometallic Chemistry 694 (2009) 1407–1418
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5.16 (2H, q, J, 6.4, 2 ꢁ CH), 4.21 (8H, m, 2 ꢁ C5H4), 4.18 (10H, s,
2 ꢁ C5H5), 1.80 (6H, d, J, 6.8, 2 ꢁ CH3); 13C NMR (CDCl3): 137.94,
130.07, 117.02, 87.69, 69.39, 68.80, 68.22, 54.83, 22.22; m/z
(FAB) 736 (M+, 53%), 279 (91), 213 (100), 188 (5), 136 (9), 121
(34). Anal. Calc. for C30H32N4PdCl2Fe2: C, 48.9; H, 4.4; N, 7.6;
[M+], 735.973756. Found: C, 48.0; H, 4.3; N, 7.4; [M+],
735.973891%.
(5.0 cm3) and dried over anhydrous sodium sulfate. The solution
was then filtered and concentrated. The product was precipitated
on addition of n-pentane (3.0 cm3) and collected as a light yellow
powder by vacuum filtration (221 mg, 85%); m.p. 124–126 °C; IR
(KBr, cmꢀ1): 3136, 2930, 2854, 1637, 1578, 1517, 1471, 1436,
1409, 1280, 1238, 1106, 1043, 1024, 1002, 853, 819, 734, 653,
618, 482; 1H NMR (CDCl3): 8.01 (2H, s, 2 ꢁ NCH), 7.42 (2H, t, J,
1.3, 2 ꢁ NCH), 6.79 (2H, t, J, 1.5, 2 ꢁ NCH), 4.11 (10H, s,
2 ꢁ C5H5), 4.06 (8H, s, 2 ꢁ C5H4), 3.89 (4H, t, J, 7.2, 2 ꢁ CH2), 2.33
(4H, t, J, 7.6, 2 ꢁ CH2), 1.76 (4H, m, 2 ꢁ CH2), 1.50 (4H, m,
2 ꢁ CH2), 1.32 (8H, m, 4 ꢁ CH2); 13C NMR (CDCl3): 139.05,
130.57, 118.71, 89.38, 68.88, 68.48, 67.50, 48.78, 31.30, 30.90,
29.89, 29.25, 26.72; m/z (FAB) 848 (M+, 38%), 335 (78), 270 (66),
199 (34), 153 (100), 136 (88), 121 (44). Anal. Calc. for
C38H48N4PdCl2Fe2: C, 53.7; H, 5.7; N, 6.6; [M+], 848.098957. Found:
C, 53.4; H, 5.6; N, 6.4; [M+], 848.098847%.
4.2.1.3. Dichlorobis(4-ferrocenylbenzyl-1H-imidazole-1-carboxylate)
palladium
[2c]. 4-Ferrocenylbenzyl-1H-imidazole-1-carboxylate
(209 mg, 0.612 mmol) and potassium tetrachloropalladate
(100 mg, 0.306 mmol) were used. A light yellow precipitate formed
as the reaction proceeded. On completion of the reaction (6 h), a
light yellow powder was collected by vacuum filtration as the
product (232 mg, 88%); m.p. 150–151 °C; IR (KBr, cmꢀ1): 3161,
3094, 1775, 1613, 1501, 1397, 1242, 1235, 1181, 1077, 1011,
824, 648, 498, 374; 1H NMR (CDCl3) 8.71 (2H, s, 2 ꢁ NCH), 7.52
(6H, m, 2 ꢁ NCH and 4 ꢁ ArH), 7.40 (2H, s, 2 ꢁ NCH), 7.35 (4H, d,
J, 7.9, ArH), 5.42 (4H, s, 2 ꢁ CH2), 4.67 (4H, s, 2 ꢁ C5H4), 4.36 (4H,
s, 2 ꢁ C5H4), 4.07 (10H, s, 2 ꢁ C5H5); 13C NMR (CDCl3): 147.43,
141.69, 140.21, 131.37, 130.72, 129.69, 126.92, 117.16, 84.59,
71.62, 70.07, 69.66, 67.07; m/z (FAB) 949 (M+, 39%), 446 (5), 385
(30), 319 (20), 274 (40), 154 (100), 136 (89); (Found: [M+],
948.992448. C42H36N4O4PdCl2Fe2 requires [M+], 948.992540).
4.2.1.7.
Dichlorobis[1-(8-ferrocenyloctyl)-1H-imidazole]palladium
[2g]. Dichlorobis[1-(8-ferrocenyloctyl)-1H-imidazole]palladium
was prepared according to the method used in Section 4.2.1.6. A
light yellow powder was obtained as the product when potassium
tetrachloropalladate (100 mg, 0.306 mmol) and 1-(8-ferrocenyloc-
tyl)-1H-imidazole (223 mg, 0.613 mmol) were used. Yield (217 mg,
78%); m.p. 109–112 °C; IR (KBr, cmꢀ1): 3137, 2926, 2855, 1636,
1516, 1432, 1410, 1274, 1237, 1103, 1047, 1021, 1001, 853, 817,
805, 733, 652, 617, 493; 1H NMR (CDCl3): 8.02 (2H, s, 2 ꢁ NCH),
7.43 (2H, s, 2 ꢁ NCH), 6.80 (2H, t, J, 1.5, 2 ꢁ NCH), 4.11 (10H, s,
2 ꢁ C5H5), 4.06 (8H, m, 2 ꢁ C5H4), 3.90 (4H, t, J, 7.2, 2 ꢁ CH2),
2.33 (4H, t, J, 7.7, 2 ꢁ CH2), 1.77 (4H, m, 2 ꢁ CH2), 1.51 (4H, m,
2 ꢁ CH2), 1.31 (16H, m, 8 ꢁ CH2); 13C NMR (CDCl3): 139.06,
130.58, 118.70, 89.81, 68.86, 68.47, 67.41, 48.83, 31.48, 30.94,
29.95, 29.84, 29.62, 29.36, 26.82; m/z (FAB) 905 (M+, 36%), 363
(58), 298 (83), 199 (46), 154 (100), 136 (93), 121 (49). Anal. Calc.
for C42H56N4PdCl2Fe2: C, 55.7; H, 6.2; N, 6.2; [M+], 905.169382.
Found: C, 55.1; H, 6.1; N, 5.8; [M+], 905.169452%.
4.2.1.4.
Dichlorobis(4-ferrocenylbenzoyl
imidazolide)palladium
[2d]. 4-Ferrocenylbenzoyl imidazolide (218 mg, 0.613 mmol) and
potassium tetrachloropalladate (100 mg, 0.306 mmol) in (1:2) eth-
anol–water (3.0 cm3) were used. A precipitate formed after 6 h of
stirring under nitrogen. The product was collected via vacuum fil-
tration as a red crystalline powder (207 mg, 76%); m.p. 138–
140 °C; IR (KBr, cmꢀ1): 3153, 3017, 1718, 1603, 1476, 1420,
1380, 1222, 1204, 1076, 901, 883, 825, 786, 759, 708, 669; 1H
NMR (CDCl3): 8.69 (2H, t, J, 1.1, 2 ꢁ NCH), 7.75 (4H, d, J, 8.5,
ArH), 7.64 (4H, d, J, 8.6, ArH), 7.62 (2H, t, J, 0.9, 2 ꢁ NCH), 7.54
(2H, t, J, 1.7, 2 ꢁ NCH), 4.78 (4H, t, J, 1.8, 2 ꢁ C5H4), 4.49 (4H, t, J,
1.8, 2 ꢁ C5H4), 4.10 (10H, s, 2 ꢁ C5H5); 13C NMR (CDCl3): 164.53,
148.76, 141.11, 131.21, 131.01, 126.89, 126.78, 117.92, 82.41,
70.92, 70.45, 67.62; m/z (FAB) 889 (M+, 21%), 356 (19), 307 (13),
289 (11), 260 (10), 154 (100), 136 (88). Anal. Calc. for
C40H33N4O2PdCl2Fe2: C, 54.0; H, 3.6; N, 6.3; [M+], 888.971411.
Found: C, 54.6; H, 3.7; N, 5.4; [M+], 888.971221%.
4.2.1.8. Dichlorobis[1-(11-ferrocenylundecanyl)-1H-imidazole]palla-
dium [2h]. The complex was prepared according to the method
used in Section 4.2.1.6. A light yellow powder was obtained as
the product of the reaction of potassium tetrachloropalladate
(100 mg, 0.306 mmol) and 1-(11-ferrocenylundecanyl)-1H-imid-
azole (249 mg, 0.613 mmol). Yield (251 mg, 83%); m.p. 91 °C; IR
(KBr, cmꢀ1): 3104, 2978, 2933, 1631, 1611, 1518, 1455, 1413,
1381, 1296, 1240, 1105, 1031, 1012, 888, 822, 822, 736, 661,
552, 507, 487; 1H NMR (CDCl3): 8.01 (2H, s, 2 ꢁ NCH), 7.42 (2H,
s, 2 ꢁ NCH), 6.79 (2H, s, 2 ꢁ NCH), 4.10 (10H, s, 2 ꢁ C5H5), 4.06
(8H, m, 2 ꢁ C5H4), 3.90 (4H, t, J, 7.3, 2 ꢁ CH2), 2.32 (4H, t, J, 7.7,
2 ꢁ CH2), 1.76 (4H, m, 2 ꢁ CH2), 1.51 (4H, m, 2 ꢁ CH2), 1.29 (28H,
m, 14 ꢁ CH2); 13C NMR (CDCl3): 139.04, 130.56, 118.71, 89.99,
68.84, 68.45, 67.37, 48.83, 31.51, 30.96, 30.04, 29.97, 29.93,
29.88, 29.74, 29.39, 26.83; m/z (FAB) 990 (M+, 18%), 511 (16),
443 (8), 406 (50), 341 (100), 307 (5), 274 (5), 199 (75), 154 (35),
121 (70); (Found: [M+], 990.271025. C48H70N4PdCl2Fe2 requires
[M+], 990.271108).
4.2.1.5. Dichlorobis(ferrocenoyl imidazolide)palladium [2e]. Ferroce-
noylimidazolide (172 mg, 0.613 mmol) and potassium tetrachloro-
palladate (100 mg, 0.306 mmol) were used. A precipitate was
observed to form after 6 h of stirring under nitrogen. The product
was collected via vacuum filtration as an orange powder
(162 mg, 72%); m.p. 213–215 °C; IR (KBr, cmꢀ1): 3151, 1692,
1446, 1380, 1291, 1209, 1095, 1080, 824, 757, 650, 503; 1H NMR
(CDCl3): 9.20 (2H, s, 2 ꢁ NCH), 7.61 (2H, s, 2 ꢁ NCH), 7.58 (2H, s,
2 ꢁ NCH), 4.97 (4H, s, C5H4), 4.77 (4H, s, C5H4), 4.42 (10H, s,
2 ꢁ C5H5); 13C NMR (CDCl3) 168.31, 140.48, 130.57, 117.23,
74.28, 72.27, 71.40, 70.29; m/z (FAB) 737 (M+, 10%), 346 (5), 307
(17), 290 (9), 192 (23), 180 (5), 154 (100), 136 (82), 120 (14);
(Found: [M+], 735.901376. C28H24N4O2PdCl2Fe2 requires [M+],
735.900985.
4.2.2. Ferrocenyl platinum complexes
4.2.2.1.
Dichlorobis[1-(ferrocenylmethyl)-1H-imidazole]platinum
[2i]. A solution of 1-(ferrocenylmethyl)-1H-imidazole (123 mg,
0.48 mmol) in dichloromethane (3.0 cm3) was added dropwise to
a solution of potassium tetrachloroplatinate (100 mg, 0.24 mmol)
in (1:2) ethanol–water (5.0 cm3). The reaction was stirred at room
temperature for 12 h under nitrogen after which an orange precip-
itate was obtained. The solid was recrystallized from dichloro-
methane/hexane solution to give yellow crystals (174 mg, 91%);
m.p. 70–72 °C; IR (KBr, cmꢀ1): 3105, 2929, 2858, 1648, 1527,
144, 1409, 1391, 1335, 1279, 1239, 1161, 1104, 1079, 1040,
4.2.1.6.
Dichlorobis[1-(6-ferrocenylhexyl)-1H-imidazole]palladium
[2f]. A solution of ethanol–water (1:2) (3.0 cm3) with potassium
tetrachloropalladate (100 mg, 0.306 mmol) was introduced into a
25 cm3 RB flask and allowed to stir. 1-(6-Ferrocenylhexyl)-1H-
imidazole (206 mg, 0.613 mmol) in dichloromethane (5 cm3) was
added slowly dropwise. The biphasic system was then stirred vig-
orously for a period of 12 h and then placed in a separating funnel.
The organic layer was separated, washed once with water