A New vic-Dioxime Ligand
179
this time the colour of the solution turned dark, and the brown-green complex was precipitated. The
product was ®ltered off, washed with water, ethanol, and diethyl ether, and dried in vacuo.
Yield: 0.17 g (62%); m.p.: >250ꢀC; MS (FAB): m/z 1401.5 [M1]; IR (KBr): ꢂ 3375 (ꢂN±H),
1
3055±3025 (ꢂCH-arom), 1720 (ꢂO±HÁ Á ÁO), 1610 (ꢂC=N), 960 (ꢂN±O) cm
.
Bis-(salicylideneiminato-nickel-1-naphthyl)-diaminoglyoximato-nickel (4; C72H50N12O8Ni3)
The reddish brown complex was prepared following the same procedure as described for the
preparation of 3 starting from 0.24 g 2 (0.39 mmol) and 0.138 g NiCl2 Á 2H2O (0.58 mmol).
Yield: 0.110 g (40%); m.p.: > 250ꢀC; IR (KBr): ꢂ 3300 (ꢂN±H), 3050-3025 (ꢂCH-arom), 1750
1
(ꢂO±HÁ Á ÁO), 1600 (ꢂC=N), 960 (ꢂN±O) cm 1; H NMR (DMSO-d6, ꢁ, 200 MHz): 16.73 (s, O±HÁ Á ÁO,
D-exchangeable), 10.30 (s, N±H, D-exchangeable), 9.03 (s, CH=N), 7.82-6.23 (m, 40Harom) ppm.
Bis-(salicylideneiminato-cobalt-1-naphthyl)-diaminoglyoximato-cobalt (5; C72H50N12O8Co3)
The dark brown complex was prepared following the same procedure as described for the
preparation of 3 starting from 0.24 g 2 (0.39 mmol) and 0.138 g CoCl2 Á 6H2O (0.58 mmol).
Yield: 0.180 g (66%); m.p.: > 250ꢀC; IR (KBr): ꢂ 3350 (ꢂN±H), 3060-3027 (ꢂCH-arom), 1700
1
(ꢂO±HÁ Á ÁO), 1605 (ꢂC=N), 960 (ꢂN±O) cm
.
Bis-(salicylideneiminato-palladium-1-naphthyl)-diaminoglyoximato-palladium
(6; C72H50N12O8Pd3)
A mixture of 0.102 g PdCl2 (0.57 mmol) and 66 mg NaCl (1.14 mmol) was dissolved in 40 cm3
ethanol. The solution was stirred at 70ꢀC until the PdCl2 was dissolved completely. A solution of
0.240 g 2 (0.38 mmol) in 209 cm3 ethanol was added to this Na2PdCl4 solution, and the procedure
described above for 3±5 was followed.
Yield: 0.170 g (56%); m.p.: >250ꢀC; IR (KBr): ꢂ 3370 (ꢂN±H), 3062-3031 (ꢂCH-arom), 1730
;
1H NMR (DMSO-d6, ꢁ, 200 MHz): 10.25 (s, N±H,
1
(ꢂO±HÁ Á ÁO), 1600 (ꢂC=N), 960 (ꢂN±O) cm
D-exchangeable), 9.01 (s, CH=N), 8.07-6.04 (m, 40Harom) ppm.
Bis-(salicylideneiminato-uranyl-1-naphthyl)-diaminoglyoximato-ꢀ-hydroxo-diuranyl
(7; C72H52N12O18U4)
To a solution of 0.120 g 2 (0.19 mmol) in 20 cm3 hot ethanol a solution of 0.161 g UO2(AcO)2 Á 2H2O
(0.38 mmol) in 10 cm3 ethanol was added. The mixture was heated on a water bath for 1 h at 50±
60ꢀC. The color of the solution became dark, and the brown complex precipitated. The precipitate
was ®ltered off, washed with hot and cold ethanol and diethyl ether, and dried in vacuo.
Yield: 0.072 g (31%); m.p.: > 250ꢀC; IR (KBr): ꢂ 3350 (ꢂN-H), 3061-3033 (ꢂCH-arom), 1640
;
1H NMR (DMSO-d6, ꢁ, 200 MHz): 11.37-11.15 (s, N-OH,
1
(ꢂC=N), 900 (ꢂO=U=O) cm
D-exchangeable), 9.41±9.14 (s, N-H, D-exchangeable), 9.20 (s, CH=N), 8.12-6.57 (m, 40Harom),
3.65 (s, ꢀ-OH, D-exchangeable)ppm.
References
[1] Welcher FJ (1947) Org Anal Reag 3: 154
[2] Hughes MN (1981) Introduction Chemistry of Biological Processes. Wiley, New York
[3] Thomas TW, Underhill AE (1972) Chem Soc Rev 1: 99
[4] Lance KA, Goldsby KA, Bush DH (1990) Inorg Chem 29: 4537
[5] Chakrovorty A (1974) Coord Chem Rev 13: 12