Synthesis and Characterization of New Mono-N-functionalized Tetraaza Macrocyclic Nickel(II) and Copper(II) Complexes

Bulletin of the Korean chemical society

Shin-Geol Kang¹  Hyunja Kim¹ 

关键词: Macrocyclic complexes;    Mono-N-functionalized macrocycle;    Functional pendant arm;    Hydrolysis;    Methanolysis;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

The reaction of bromoacetonitrile with 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.12.6.01.18.07.12]tricosane (L10) containing a N-CH2-N linkage produces 17-cyanomethyl-3,14-dimethyl-2,6,13,17-tetraazatetracyclo- [16.4.12.6.01.18.07.12]tricosane (L11). The mono-N-functionalized macrocyclic complexes [ML2]2+ (M = Ni(II) or Cu(II); L2 = 2-cyanomethyl-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.0.07.12]docosane) can be prepared by the reaction of L11 with nickel(II) or copper(II) ion in acetonitrile. The N-CH2CN group attached to [ML2]2+ readily reacts with water or methanol to yield the corresponding complexes of HL3 bearing one N-CH2CONH2 pendant arm or L4 bearing one N-CH2C(=NH)OCH3 group. The N-CH2CONH2 or N-CH2C(=NH)OCH3 group of each complex is coordinated to the central metal ion. Both [NiL4(H2O)]2+ and [CuL4]2+ are quite stable in acidic aqueous solutions, but undergo hydrolysis to yield [Ni(HL3)(H2O)]2+ or [Cu(HL3)]2+ in basic aqueous solutions. In contrast to [Cu(HL3)]2+, [Ni(HL3) (H2O)]2+ is readily deprotonated to form [NiL3 (H2O)]+ (L3 = a deprotonated form of HL3) in basic aqueous solutions.

【 授权许可】

Unknown