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Dioxouranium (Ⅵ) 이온과 N_2O_2系 거대 고리 Iigand 와의 錯物 形成
具昌賢,金始中 단국대학교 대학원 1985 學術論叢 Vol.9 No.-
The macrocyclic ligands with N_2O_2 donor sets, such as 3, 4 : 9, 10-dibenzo-1, 12-diaza-5, 8-dioxacyclotetradecane (Oen-Nen-H_4), 3, 4 : 9, 10-dibenzo-1, 12-diaza-5, 8-dioxacyclotetradecane (Oen-Ntn-H_4), 3, 4 : 10, 11-dibenzo-1, 13-diaza-5, 9-cyclopentadecane (Otn-nen-H_4) and 3, 4 : 10, 11-dibenzo-1, 13-diaza-5, 9-dioxacyclohexadecane (Otn-Ntn-H_4) have been synthetized as the reported method, while the synthetic method of 3, 4 ; 10, 11-dibenzo-1, 8-diaza-5, 12-dioxacyclotetradecane (Trans Mcen-H_4) were devised. Dioxouranium (Ⅵ) complexes with the ligands have been characterized in methanol solution by UV-Vis-and IR-spectrophotometry, and the protonation constants of the ligands and the stability constants of the complexes have been determined by potentiometry at 25℃ with a empirical equation ??/??-1) M=(2-??) Mβ_2(??-1)-β_1. The compositions of the complexes are (UO_2^2+)_2 (Oen-Nen-H_4), (UO_2^2+) (Oen-Ntn-H_4), UO_2^2+(Otn-Nen-H_4), (UO_2^2+) (Otn-Ntn-H_4) and (UO_2^2+)_2 (trans Mean-H_4). For the complexes, the stabilities reach a peak at the 16-membered ring complex, and consideration of structural factors suggests that each ligand is tetradenate to dioxouranium (Ⅵ) ion in which two oxygen and two nitrogen atoms coordinate to metal ion respectively and that Trans-N_2O_2 system ligand forms more stable complex than Cis-N_2O_2 system ligand.