Ranford John D., Vittal Jagadese J., Wang Yu M.
Department of Chemistry, National University of Singapore, Lower Kent Ridge Road, Singapore 119260.
Inorg Chem. 1998 Mar 23;37(6):1226-1231. doi: 10.1021/ic970805g.
Salicylaldehyde hydrazones derived from acyldicarboxylic acids (H(4)L(n)(), where n = 0, 1, 2, 4, 6, 8, 10, 14 and is the number of methylene units) of varying chain length have been prepared, and their dicopper(II) complexes have been isolated as bis analogues of antitumor carboxylate hydrazones. The predominant structural form adopted is polymeric, with [{Cu(2)L(n)()}(m)()] formed in neutral or basic solution, [{Cu(2)(H(2)L(n)())Cl(2)}(m)()] from dilute HCl, and [{Cu(2)(H(2)L(n)())}(m)()].(ClO(4))(2)(m)() from dilute HClO(4). The crystal structures of [Cu(2)(H(2)L(1))(H(2)O)(2)].(ClO(4))(2).3H(2)O and [{Cu(2)(H(2)L(4))(C(2)H(5)OH)(2)}(m)()].(ClO(4))(2)(m)().m(C(2)H(5)OH) have been determined. The structure of [Cu(2)(H(2)L(1))(H(2)O)(2)]. (ClO(4))(2).3H(2)O consists of discrete di-Cu(II) molecules with nonsymmetry-related Cu(II) centers. The copper atoms are square-planar with H(2)L(1) supplying two tridentate, monoanionic ONO domains and water completing the coordination sphere. The two metal-binding domains are inclined at 80 degrees to each other. For [{Cu(2)(H(2)L(4))(C(2)H(5)OH)(2)}(m)()].(ClO(4))(2)(m)().m(C(2)H(5)OH) the symmetry-related copper atoms are square-pyramidal with the base composed of H(2)L(4), acting as a tridentate ONO chelator, and an O-bonded ethanol molecule. Axial phenolato bridges complete the coordination sphere, linking molecules to give a polymer. Compounds prepared have been characterized by a range of physicochemical and spectroscopic techniques, and proton and metal ion stability constant data have been determined.
已制备了由不同链长的酰基二羧酸(H(4)L(n),其中n = 0、1、2、4、6、8、10、14,n为亚甲基单元数)衍生的水杨醛腙,并分离出它们的二铜(II)配合物,作为抗肿瘤羧酸腙的双类似物。所采用的主要结构形式是聚合物,在中性或碱性溶液中形成[{Cu(2)L(n)} (m)],在稀盐酸中形成[{Cu(2)(H(2)L(n))Cl(2)} (m)],在稀高氯酸中形成[{Cu(2)(H(2)L(n))} (m)].(ClO(4))(2)(m)。已测定了[Cu(2)(H(2)L(1))(H(2)O)(2)].(ClO(4))(2).H(2)O和[{Cu(2)(H(2)L(4))(C(2)H(5)OH)(2)} (m)].(ClO(4))(2)(m).m(C(2)H(5)OH)的晶体结构。[Cu(())()()].(ClO(4))(2).H(2)O的结构由具有非对称相关Cu(II)中心的离散二铜(II)分子组成。铜原子为平面正方形,H(2)L(1)提供两个三齿单阴离子ONO域,水完成配位球。两个金属结合域彼此倾斜80度。对于[{Cu(2)(H(2)L(4))(C(2)H(5)OH)(2)} (m)].(ClO(4))(2)(m).m(C(2)H(5)OH),对称相关的铜原子为四方锥,底面由作为三齿ONO螯合剂的H(2)L(4)和一个O键合的乙醇分子组成。轴向酚盐桥完成配位球,连接分子形成聚合物。所制备的化合物已通过一系列物理化学和光谱技术进行了表征,并测定了质子和金属离子稳定性常数数据。