CuII Complexes of b-Ketoenaminic Ligands
2143±2157
1
615 cm
(vs); UV/Vis (MeOH):
l
(e) 659 (319), 357 nm
(0.86 g, 4.64 mmol), respectively, in methanol (10 mL) were added drop-
wise. The solution was heated under reflux for 1 h, and was then allowed to
stand overnight. The ligands were then precipitated by the addition of
diethyl ether to yield colorless powders.
(2530mol 1 dm3 cm 1); MS (DEI): m/z: 967 [M] , 908 [M OAc] , 849
[M 2 Â OAc] , 785 [Cu2L2] , 515 [Cu2L(OAc)] , 452 [CuL(OAc)] , 393
[CuL] ; elemental analysis calcd (%) for C34H54N2O18Cu3 (967.42): C 42.21,
H 5.42, N 2.90, Cu 19.7; found C 41.79, H 5.54, N 2.87, Cu 19.5.
Ligand H24a (1 g, 3.46 mmol) or H24c (1 g, 3.13 mmol) were dissolved in
methanol (15 mL) and triethylamine (0.96 mL, 6.92 mmol) or (0.87 mL,
6.26 mmol), respectively, was added. This solution was added dropwise to a
suspension of copper(ii) acetate monohydrate (0.69 g, 3.46 mmol or 0.62 g,
3.13 mmol, respectively) in methanol (5 mL). The dark blue solution was
stirred for 30 minutes. Diethyl ether was added and a blue powder
precipitated. This was identified to be pure Cu(4a) or Cu(4c), respectively.
Yield: 2.00 g (67%) [Cu(4a)] and 2.09 g (72%) [Cu(4c)].
Bis[1,2,3-O-trimethyl-6-N-(2,2-bisethylcarboxyethylene)amino-6-deoxy-
glucopyranoso]bis-m-acetatotricopper(ii), Cu(1b): Cu(1b) was isolated in a
similar manner to Cu(1a). Yield: 174 mg (33.9%); IR (KBr): nÄ 3436 (w),
3279 (w), 2980 (s), 2934 (s), 2907 (s), 2836 (w), 1702 (s), 1684 (s), 1657 (s),
1613 (vs),1553 (s), 1499 (w), 1553 (s), 1430 (s), 1399 (w), 1379 (w), 1346 (w),
1272 (w), 1244 (s), 1218 (s), 1156 (w), 1139 (w), 1061 (vs), 1047 (vs), 1024
1
(vs),959 (s), 918 (w), 802 (s), 791 (s), 734 (s), 621 cm (w); UV/Vis
(toluene): l (e) 664 (435), 397 (1469), 346 nm (1773mol 1 dm3 cm 1); MS
Cu(4a): IR [KBr (4000 ± 450cm 1), Nujol (450 ± 50cm 1)]: nÄ 3392 (s),
2923 (s), 2700 (m), 1683 (w), 1615 (s), 1570 (s), 1508 (w), 1457 (m), 1392 (s),
1357 (m), 1285 (m), 1099 (m), 1084 (m), 1026 (s), 992 (s), 940 (m), 858 (m),
843 (m), 803 (m), 765 (m), 735 (w), 654 (s), 616 (m), 593 (m), 543 (w), 485
(w), 427 (w), 365 (w), 322 (w), 303 (w), 286 (w), 259 (s), 226 (w), 172 (w),
162, (m), 105 (w), 96 cm 1 (m); UV/Vis (MeOH): l (e) 660 (161), 360 nm
(FAB): m/z: 1028 [Cu3L2(OAc)] , 969 [Cu3L2] , 905 [Cu2L2] , 453 [CuL] ,
392 [H2LH] ; elemental analysis calcd (%) for C38H60N2O22Cu3 (1087.53):
C 42.08, H 5.49, N 2.73, Cu 18.6; found C 42.39, H 5.39, N 2.77, Cu 18.5.
Bis[1,2-O-isopropylidene-5-N-(3-acetylbut-3-en-2-one)amino-5-deoxyglu-
cofuranoso]aquodicopper(ii)-bis[1,2-O-isopropylidene-5-N-(3-acetylbut-3-
en-2-one)amino-5-deoxyglucofuranoso]-methanolodicopper(ii) ´ 3H2O,
Cu(2a): Isolation of Cu(2a): The residue was dissolved in toluene. A violet
toluene-containing compound crystallized during the slow evaporation of
the solvent. Recrystallization from water/methanol 1:1 led to the
precipitation of Cu(2a) in a quality suitable for X-ray crystal-structure
determination. Yield: 50 mg (24.00%); IR (KBr): nÄ 3331 (w), 2984 (s),
2928 (s), 1719 (vw), 1649 (w), 1584 (vs), 1457 (s), 1395 (vs), 1357 (s), 1283
(s), 1257 (s), 1213 (s), 1165 (s), 1125 (s), 1059 (vs), 1008 (vs), 946 (s), 882 (s),
844 (s), 732 (s), 696 (w), 638 cm 1 (s); UV/Vis (MeOH): l (e) 651 (166),
(879 mol 1 dm3 cm 1); MS (ESI) m/z: 1051 [Cu3L3H] , 803
[Cu2L2HNEt3] ,
723
[Cu2L2Na] ,
701
[Cu2L2H] ,
383
[CuL(MeOH)H] , 333 [Cu(L H2OH] , 102 [HNEt3] ; elemental
analysis calcd (%) for C32H53N3O16Cu2 (862.87): C 44.54, H 6.19, N 4.87, Cu
14.7%; found C 43.84; H 6.34; N 4.91; Cu 14.8.
Cu(4c): IR [KBr (4000 ± 450cm 1), Nujol (450 ± 50cm 1)]: nÄ 3395 (s),
2979 (vs), 2944 (vs), 2739 (s), 2672 (vs), 2622 (vs), 2605 (s), 2531 (m), 2498
(s), 1691 (s), 1614 (s), 1572 (m), 1476 (s), 1444 (m), 1398 (s), 1365 (m), 1331
(w), 1271 (m), 1186 (w), 1172 (m), 1094 (m), 1071 (s), 1037 (vs),915 (w), 851
(m), 807 (m), 774 (m), 638 (w), 597 (w), 539 (w), 462 (w), 427 (w), 365 (w),
373 nm (1344 mol 1 dm3 cm 1); MS (ESI): m/z: 1585 [Cu4L4Na] , 1173
[Cu3L3H] , 804 [Cu2L2Na] , 783 [Cu2L2H2] , 423 [CuL(MeOH)] , 391
1
322 (w), 303 (w), 286 (w), 259 (s), 226 (w), 172 (w), 162 (m), 105 (w), 96 cm
[CuL] ; elemental analysis calcd (%) for C61H96N4O33Cu4 (1667.62): C
(m); UV/Vis (MeOH): l (e) 646 (148), 350 nm (2700 mol 1 dm3 cm 1);
43.94, H 5.80, N 3.36, Cu 15.2; found C 44.05, H 5.87, N 3.31, Cu 15.1.
MS (ESI): m/z: 1545 [Cu4L4Na] , 1165 [Cu3L3Na] , 783 [Cu2L2Na] ,
Bis[1,2-O-isopropylidene-5-N-(2,2-bisethylcarboxyethylene)amino-5-de-
oxyglucofuranoso]dicopper(ii), Cu(2b): The residue was extracted with
toluene to give a blue solid. Yield: 110 mg (49%); IR (KBr): nÄ 3426 (vw),
2955 (s), 2923 (vs), 2854 (vs), 1733 (vw), 1675 (w), 1604 (s), 1461 (s), 1412
(w), 1377 (s), 1347 (w), 1259 (s), 1215 (w), 1166 (w), 1068 (vs), 1013 (vs), 868
761 [Cu2L2H] , 445 [CuL(MeOH)2H] , 413 [CuL(MeOH)H] , 381
[CuLH] , 102 [HNEt3] ; elemental analysis calcd (%) for C34H57N3O18-
Cu2 (922.93): C 44.24, H 6.22, N 4.55, Cu 13.7; found C 43.58, H 6.50, N 4.45,
Cu 13.6.
3-[N-(2-Hydroxycyclohexyl)aminomethylene]-2,4-pentadione
(H25a):
1
(w), 796 (vs), 727 (w), 642 cm (w); UV/Vis (toluene): l (e) 583 (466),
trans-Cyclohexanolammonium chloride (3.04 g, 0.02 mol) was suspended
in chloroform (20 mL). Triethylamine (4.04 g, 0.04 mol) was added, and the
solution was stirred for 30 minutes. 3-Ethoxymethylene-2,4-pentandione
(3.12 g, 0.02 mol) in chloroform (10 mL) was added, and the mixture was
heated under reflux for 2 h. After cooling, diethyl ether was added to the
solution. The triethylammonium chloride precipitate was filtered off. After
evaporation of the solvent, the remaining oil was purified by recrystalliza-
tion from an ethanol/water mixture. Yield: 3.56 g (79%). 1H NMR
(200 MHz, CDCl3, 258C, TMS): d 10.94 (dd, 1H; N H), 8.40 (d, 1H;
352 nm (2794 mol 1 dm3 cm 1); MS (ESI): m/z: 2728 [Cu6L6Na] , 1827
[Cu4L4Na] , 1353 [Cu3L3] , 925 [Cu2L2Na] ; elemental analysis calcd
(%) for C34H50N2O18Cu2 (901.86): C 45.28, H 5.59, N 3.11, Cu 14.1; found C
45.47, H 5.48, N 3.21, Cu 14.1.
Bis[1,2-O-isopropylidene-6-N-(3-acetylbut-3-en-2-one)amino-6-deoxyglu-
cofuranoso]dicopper(ii), Cu(3a): Cu(3a) was isolated by recrystallization
of the residue from a mixture of toluene, chloroform, and ethanol (2:2:1).
Yield: 122 mg (62%); IR (KBr): nÄ 3314 (w), 2961 (s), 2925 (vs), 2854 (s),
2683 (vw), 1724 (w), 1650 (w), 1585 (vs), 1448 (s), 1387 (vs), 1310 (w), 1259
CH ), 3.41 (m, 2H; CH2), 2.97 (m, 2H; CH2), 2.39 (m, 1H; CH), 2.34 (s,
(s), 1214 (w), 1163 (w), 1067 (vs), 1010 (vs),955 (w), 852 (w), 798 (s), 732
3H; CH3), 2.32 (dd, 1H), 2.20 (s, 3H; CH3), 1.95 (m, 2H; CH2), 1.78 (m,
2H; CH2); 13C NMR(PENDANT, 200 MHz, CDCl3, TMS): d 199 (quart.
C), 195 (quart.C), 160 (CH), 110 (quart. C), 74 (CH), 65 (CH), 46 (CH2), 34
(CH2), 31.5 (CH3), 31 (CH2), 26 (CH3), 24 (CH2); IR (KBr): nÄ 3487 (s),
2982 (s), 2937 (s), 2861 (s), 2757 (m), 2739 (w), 2677 (w), 2603 (w), 2450 (w),
1680 (vs), 1635 (vs), 1583 (s), 1476 (m), 1427 (s), 1388 (s), 1360 (s), 1302 (m),
1258 (s), 1241 (s), 1195 (w), 1142 (m), 1120 (w), 1077 (s), 1021 (m), 975 (m),
953 (w), 939 (w), 865 (m), 822 (s), 764 (m), 724 (w), 590 (m), 549 (m),
474 cm 1 (w); elemental analysis calcd (%) for C12H19NO3 (225.29): C 63.97,
H 8.50, N 6.21; found C 63.76, H 8.39, N 6.24.
1
(vw), 617 cm
(vw); UV/Vis (toluene):
l
(e) 620 (345), 365 nm
(1429 mol 1 dm3 cm 1); MS (ESI): m/z: 781 [Cu2L2] , 720 [CuL2H2] , 423
[CuL(MeOH)] , 391 [CuL] ; elemental analysis calcd (%) for
C30H42N2O14Cu2 (781.76): C 46.09, H 5.42, N 3.58, Cu 16.3; found C 45.67,
H 5.38, N 3.36, Cu 16.1.
Bis[1,2-O-isopropylidene-6-N-(2,2-bisethylcarboxyethylene)amino-6-de-
oxyglucofuranoso]dicopper(ii), Cu(3b): The isolation of Cu(3b) was
carried out in an analogous manner to that of Cu(3a). Yield: 144 mg
(66%); IR (KBr): nÄ 3434 (w), 2980 (s), 2933 (s), 2902 (s), 1738 (w), 1714
(w), 1686 (w), 1653 (vs), 1616 (vs), 1570 (vs), 1503 (w), 1441 (s), 1426 (s),
1376 (s), 1342 (s), 1286 (s), 1212 (s), 1166 (s), 1122 (s), 1064 (vs), 1009
Tetrakis-{3-[N-(2-oxycyclohexyl)aminatomethylene]-2,4-pentanedione-
(2-)O2',N,O2}tetracopper(ii), Cu(5a): Solid copper acetate monohydrate
(0.80 g, 4 mmol)was added to H25a (0.91 g, 4 mmol) in chloroform (20 mL).
After addition of triethylamine (20 drops), the copper salt dissolved and
the solution turned deep blue. The solution was allowed to stand in an open
round flask for 2 d to yield deep blue crystals. Crystals in quality suitable for
X-ray crystal structure analysis were obtained by the addition of pyridine
(10 mL) before the solvent was allowed to evaporate. Yield: 0.46 g
(36.4%); IR [KBr (4000 ± 450cm 1), Nujol (450 ± 50cm 1)]: nÄ 3433 (m),
3252 (w/sh), 2930 (vs), 2857 (vs), 1735 (w), 1654 (s), 1607 (vs), 1507 (w),
1467 (s), 1400 (vs), 1355 (m), 1275 (s), 1236 (s), 1209 (w), 1179 (w), 1145
(m), 1124 (w), 1081 (m), 1064 (m), 1027 (m), 990 (m), 940 (m), 921 (m), 890
(w), 858 (m), 801 (w), 756 (w), 670 (m), 635 (s), 622 (m), 591 (m), 551 (m),
460 (m), 422 (m), 362 (m), 332 (w), 317 (w), 286 (m), 259 (s), 176 (w/sh), 168,
1
(vs),847 (s), 803 (w), 785 (w), 732 (w), 677 cm (w); UV/Vis (toluene): l
(e) 626 (601), 346 nm (3172 mol 1 dm3 cm 1); MS (ESI): m/z: 933
[Cu2L2(MeOH)] , 452 [CuLH] ; elemental analysis calcd (%) for
C34H50N2O18Cu2 (901.86): C 45.28, H 5.59, N 3.11, Cu 14.1; found C:
45.47%, H: 5.48%, N: 3.21%, Cu: 14.1%.
Triethylammonium bis[2-N-(3-acetylbut-3-en-2-one)amino-2-deoxygluco-
pyranoso-m-acetato]dicuprate(ii), Cu(4a), and triethylammonium bis[2-N-
(3-ethylcarboxylbut-3-en-2-one)amino-2-deoxyglucopyranoso-m-acetato]-
dicuprate(ii), Cu(4c): 2-Amino-2-deoxy-glucopyranose hydrochloride (1 g,
4.64 mmol) was suspended in methanol (10 mL), and triethylamine
(1.29 mL, 9.28 mmol) was added. 3-Ethoxymethylene-2,4-pentandione
(0.72 g, 4.64 mmol) or 3-ethoxy-2-acetyl-prop-2-ene acid ethyl ester
Chem. Eur. J. 2001, 7, No. 10
ꢀ WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2001
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