N、N'-[(邻羧基)亚苄基]乙二胺及其类似物与铜离子的配位反应

THE COORDINATION AND COMPOSITION OF COPPER COMPLEXES CHELATED WITH N,N'-BIS[E(2-CARBOXYL) BENZILIDENE]ETHYLENEDIAMINE AND ITS ANALOGS

用醛与胺缩合制备了标题试剂(H_2L^1)及其类似物(H_2L^2～H_2L^7,L^8)研究了它们的表征及其在溶液中与Cu^(2+)的反应,以及固体配合物的组成与结构。

The title reagents and its analogs were synthesised by condensed the aldehydes with diamines. Two series of copper complex(Cu:ligand=1:1 and 1:2) were obtained in solution. λ_(max) of blue (1:1)complexare 661, 665 and 665 nm and the violet (1:2): 548, 558 and 559 nm forH_2L^1, H_2L^3 and L^8 respectively. The coordinative power greatly decreaseswhen the -CH_2CH_2-group (H_2L^1) H_2L^3) was displaced by (?)group(H_2L^2, H_2L^4) due to the electron density of donor nitrogen atoms decreas-ing.7 crystals: CuL^3·2H_2O(blue), CuL^3(bright green), Cu_3L_2~5(NO_3)_2·4H_2O(blue), Cu_2L^2(NO_3)_2·2H_2O(blue), Cu_2L^7(NO_3)_2·2H_2O(blue), CuL^7(NO_3)_2·2H_2O(blue), CuL^8SO_4(blue) and CuL_2~8SO_4(violet) were obtained. Thepossible stractures of these compounds were suggested according to theinformations given by the results of differential thermoanalysis and IRspectra. In addition to nitrogen and other oxygen atoms, the oxygen atomsof crystal water also act as the donor. But the coordination of carboxylgroup is different, in the waterless CuL^3 obtained from alkaline solution,it acts as a dentate but not in CuL^3·2H_2O crystallizing in acid medium,these sites were occupied by crystal water. It may be expected the ester-ified carboxyl didn't coordinate with Cu. Moreover, NO_3^- and SO_4^(2-) bothact as counter in crystals. The coordination number of Cu in the threecomplexes obtained from L^8 and H_2L^6 is 4 and in all of the other com-plexes, the coordination number is 6.