A.R. Stefankiewicz et al. / Polyhedron 29 (2010) 178–187
185
2H, J = 8.2 Hz), 6.94 (d, 1H, J = 6.9 Hz), 6.88 (t, 1H, J = 8.5 Hz) ppm.
IR (KBr): = 3357 (OH), 3063 (CH arom), 3029 (CH imin), 1631
of ether. ESI-MS(+): m/z = 569 (100) [Co(HL2)(L2)]+. ESI-MS(-): m/
z = 245 (35) [Co(NO3)3]À, 153 (20) [Co(NO3)4]2-. IR (KBr):
m
m =
(CN), 1596 (py), 1569 (py), 1554(py), 1482 (py), 1465 (py), 1420
(NO3À), 1385 (NO3À), 1372 (NO3À), 1315 (NO3À), 1300 (py), 1277
(py), 1154 (py), 863 (OH), 803 (NO3À), 777 (py), 746 (py), 588
3405 (OH), 3068 (CH arom), 3006 (CH imin), 2950 (CH3), 1715
(C@O), 1606 (CN), 1580 (py), 1565 (py), 1515 (py), 1461 (py),
1437 (NO3À), 1417 (NO3-), 1385 (NO3À), 1310 (NO3-), 1289 (py),
1227 (CO), 1188 (py), 1160 (py), 886 (OH), 800 (NO3À), 768 (py),
746 (py), 580 (py), 512 (py) cmÀ1. Anal. Calc. for [Co(HL2)(L2)]2
[Co(NO3)4] (1447.83): C, 46.46; H, 3.20; N, 11.61. Found: C,
46,43; H, 3.24; N, 11.60%.
(py) cmÀ1
.
Anal. Calc. for [Zn(HL1)(L1)]2[Zn(NO3)4]Á2CH3CN
(1312.09): C, 47.42; H, 3.37; N, 14.89. Found: C, 47.50; H, 3.37;
N, 14.85%.
4.9. Ag(I) complex (2a)
4.13. Zn(II) complex (2e)
A mixture of AgNO3 (4.4 mg, 26
mol) in CH3CN (10 mL) was stirred at room temperature for
l
mol) and ligand HL2 (13.4 mg,
52
l
A mixture of Zn(NO3)2Á6H2O (9.6 mg, 30
(15.5 mg, 60 mol) in CH3CN (10 mL) was stirred at room temper-
l
mol) and ligand HL2
24 h. The yellow complex 2a was isolated in quantitative yield
by evaporation of the solvent and recrystallisation of the residue
from the minimum volume of CH3CN by the gradual addition of
ether. ESI-MS: m/z = 621 (70) [Ag(HL2)2]+, 363 (40) [Ag(HL2)]+. 1H
NMR (300 MHz, CD3CN): d = 10.00 (s, 1H, OH), 8.79 (m, 2H,
J = 4.4 Hz), 8.24 (d, 1H, J = 7.1 Hz), 7.95 (t, 1H, J = 8.8 Hz), 7.64 (t,
1H, J = 3.0 Hz), 7.38 (d, 1H, J = 8.2 Hz), 7.30 (s, 1H), 6.68 (d, 1H,
l
ature for 24 h. The orange complex 2e was isolated in quantitative
yield by evaporation of the solvent and recrystallisation of the res-
idue from the minimum volume of CH3CN by the gradual addition
of ether. ESI-MS(+): m/z = 575 (10) [Zn(HL2)(L2)]+, 319 (75)
[Zn(L2)]+, 257 (10) [H2L2]+. ESI-MS(-): m/z = 156 (50) [Zn(NO3)4]2À
.
1H NMR (300 MHz, CD3CN): d = 10.01 (s, 1H, OH), 8.97 (s, 1H, H–
C@N), 8.96 (d, 1H, J = 1.2 Hz), 8.17 (d, 1H, J = 2.0 Hz), 8.00 (t, 1H,
J = 6.0 Hz), 7.51 (d, 1H, J = 1.2 Hz), 7.49 (m, 2H, J = 2.4 Hz), 7.38
J = 8.2 Hz), 3.85 (s, 3H, OCH3) ppm. IR (KBr)
m = 3340 (OH), 3103
(CH arom), 2951 (CH imin), 2924 (CH3), 1707 (C@O), 1605 (CN),
1529 (py), 1490 (py), 1437 (py), 1384 (NO3-), 1295 (py), 1227
(CO), 1097 (py), 890 (OH), 796 (NO3-), 766 (py), 747 (py), 580
(py) cmÀ1. Anal. Calc. for [Ag(HL2)2]NO3 (682.39): C, 49.28; H,
3.54; N, 10.26. Found: C, 49.30; H, 3.55; N, 10.25%.
(d, 1H, J = 2.0 Hz), 3.90 (s, 3H, OCH3) ppm. IR (KBr):
m = 3333
(OH), 3065 (CH arom), 3026 (CH imin), 2951 (CH3), 1716 (C@O),
1616 (CN), 1595 (py), 1569 (py), 1480 (py), 1440 (NO3À), 1384
(NO3À), 1310 (NO3À), 1290 (py), 1229 (CO), 1157 (py), 1125 (py),
896 (OH), 795 (NO3À), 778 (py), 766 (py), 747 (py), 538 (py), 514
4.10. Cu(II) complex (2b)
(py) cmÀ1 Anal. Calc. for [Zn(HL2)(L2)]2[Zn(NO3)4](CH3CN)2
.
(1549.31): C, 46.51; H, 3.38; N, 12.66. Found: C, 46.50; H, 3.40;
N, 12.65%.
A mixture of [Cu(CH3CN)4]PF6 (7.1 mg, 19
(9.7 mg, 38 mol) in CH3CN (10 mL) was stirred at room tempera-
l
mol) and ligand HL2
l
ture for 24 h under the normal atmosphere. The brown–red com-
plex 2b was isolated in quantitative yield by evaporation of the
solvent and recrystallisation of the residue from the minimum vol-
ume of CH3CN by the gradual addition of ether. ESI-MS: m/z
4.14. Ag(I) complex (3a)
A mixture of AgNO3 (3.3 mg, 19
lmol) in CH3CN (10 mL) was stirred at room temperature for
l
mol) and ligand HL3 (9.8 mg,
38
(%) = 574 (70) [Cu(HL2)(L2)]+, 319 (80) [Cu(L2)]+. IR (KBr)
m
= 3378
24 h. The yellow complex 3a was isolated in quantitative yield
by evaporation of the solvent and recrystallisation of the residue
from the minimum volume of CH3CN by the gradual addition of
ether. ESI-MS: m/z = 619 (10) [Ag(HL3)2]+, 364 (40) [Ag(HL3)]+. 1H
NMR (300 MHz, CD3CN): d = 10.01 (s, 1H, OH), 8.98 (s, 1H, H–
C@N), 8.79 (d, 1H, J = 4.9 Hz), 8.69 (d, 1H, J = 4.7 Hz), 8.01 (d, 1H,
J = 3.8 Hz), 7.97 (t, 1H, J = 8.8 Hz), 7.87 (t, 1H, J = 7.4 Hz), 7.35 (s,
1H), 7.03 (d, 1H, J = 8.2 Hz), 3.85 (s, 3H, OCH3) ppm. IR (KBr):
(OH), 3077 (CH arom), 3040 (CH imin), 2952 (CH3), 1724 (C@O),
1602 (CN), 1588 (py), 1567 (py), 1481 (py), 1438 (py), 1307 (py),
1295 (py), 1226 (CO), 1158 (py), 1127 (py), 877 (OH), 847 (PF6-),
778 (py), 767 (py), 747 (py), 559 (py), 516 (py) cmÀ1. Anal. Calc.
for [Cu(HL2)(L2)]PF6 (721.02): C, 46.64; H, 3.36; N, 7.77. Found: C,
46.62; H, 3.30; N, 7.77%.
4.11. Cu(II) complex (2c)
m = 3360 (OH), 3082 (CH arom), 3017 (CH imin), 2951 (CH3),
1704 (C@O), 1620 (CN), 1592 (py), 1567 (py), 1512 (py), 1474
(py), 1434 (py), 1384 (NO3-), 1289 (py), 1274 (py), 1228 (CO),
1165 (py), 1132 (py), 1102 (py), 883 (OH), 800 (NO3-), 780 (py),
763 (py), 745 (py), 508 (py) cmÀ1. Anal. Calc. for [Ag(HL3)2]NO3
(682.39): C, 49.28; H, 3.54; N, 10.26. Found: C, 49.31; H, 3.53; N,
10.27%.
A mixture of Cu(NO3)2Á6H2O (7.4 mg, 27.0
(13.7 mg, 54.0 mol) in CH3CN (10 mL) was stirred at room tem-
l
mol) and ligand HL2
l
perature for 24 h. The dark red complex 2c was isolated in quanti-
tative yield by evaporation of the solvent and recrystallisation of
the residue from the minimum volume of CH3CN by the gradual
addition of ether. ESI-MS: m/z (%) = 572 (30) [Cu(HL2)(L2)]+, 318
(100) [Cu(L2)]+. IR (KBr):
m
= 3368 (OH), 3068 (CH arom), 3023
4.15. Cu(II) complex (3b)
(CH imin), 2955 (CH3), 1716 (C@O), 1645 (CN), 1569 (py), 1537
(py), 1482 (py), 1465 (py), 1384 (NO3À), 1301 (py), 1289 (py),
1264 (py), 1233 (CO), 1117 (py), 894 (OH), 797 (NO3À), 780 (py),
768 (py), 747 (py), 518 (py) cmÀ1. Anal. Calc. for [Cu(HL2)(L2)]NO3
(637.06): C, 52.79; H, 3.64; N, 10.99. Found: C, 52.80; H, 3.63; N,
11.00%.
A mixture of [Cu(CH3CN)4]PF6 (9.6 mg, 26
(13.3 mg, 52 mol) in CH3CN (10 mL) was stirred at room temper-
l
mol) and ligand HL3
l
ature for 24 h under the normal atmosphere. The brown complex
3b was isolated in quantitative yield by evaporation of the solvent
and recrystallisation of the residue from the minimum volume of
CH3CN by the gradual addition of ether. ESI-MS m/z (%) = 574
4.12. Co(II) complex (2d)
(70) [Cu(HL3)(L3)]+, 319 (20) [Cu(L2)]+. IR (KBr)
m = 3399 (OH),
3060 (CH arom), 3028 (CH imin), 2953 (CH3), 1710 (C@O), 1592
(py), 1566 (py), 1493 (py), 1471 (py), 1432 (py), 1295 (py), 1235
(CO), 1194 (py), 1121 (py), 880 (OH), 852 (PF6-), 765 (py), 740
(py), 557 (py), 510 (py) cmÀ1. Anal. Calc. for [Cu(HL3)(L3)] PF6
(721.02): C, 46.64; H, 3.36; N, 7.77. Found: C, 46.63; H, 3.33; N,
7.75%.
A mixture of Co(NO3)2Á6H2O (7.5 mg, 26
(13.2 mg, 52 mol) in CH3CN (10 mL) was stirred at room temper-
ature for 24 h. The red complex 2d was isolated in quantitative
yield by evaporation of the solvent and recrystallisation of the res-
idue from the minimum volume of CH3CN by the gradual addition
l
mol) and ligand HL2
l