冠醚化双西佛碱钴(Ⅱ)配合物的合成、氧合和催化氧化性能 研究

合成和表征了三个新的冠醚化双西佛碱4',5'-双(2-羟基苯亚甲基亚氨基)苯并-12-冠-4(L^1H2),4',5'-双(5-氯-2-羟基苯亚甲基亚氨基)苯并-12-冠-4(L^1H2)和4',5'-双(5-溴-2-羟基苯亚甲基亚氨基)苯并-12-冠-4(L^3H2)以及它们的钴配合物。在吡啶溶液中和不同温度下，测定了配合物的饱和吸氧量，求出了它们的氧加合常数和热力学参数△H°,△S°,并以这些配合物为催化剂，活化分子氧氧化环已烯制备环已烯酮，通过与未冠醚化的类似物作比较，讨论了冠醚环的引入对配合物与氧分子加合性能以及催化氧化性能的影响。

Synthesis, oxygenation and catalytic activity of crowned bis-schiff bases cobalt complexes

Three new crowned bis-Schiff bases, 4',5'-bis(2- hydroxyphenylmethylideneimino)benzo-12-crown- 4(L^1H2),4',5'-bis(5- chloro-2-hydroxyphenylmethylideneimino) benzo-12-crown-4(L^2H2),4',5'- bis(5-bromo-2- hydroxyphenylmethylideneimino)benzo-12-crown-4(L^3H2) and their cobalt(Ⅱ) complexes(1,2,3) were prepared and characterized by MS,IR, NMR and elemental analysis. The stoichiometries of dioxygen uptake by the Co complexes were measured in pyridine solution. The equilibrium constants and thermodynamic parameters of oxygenation (△H°, △S°) were calculated. The catalytic activity and selectrivity of the cobalt complexes in cyclohexene oxidation were examined. The influence of the crown ether ring on dioxygen affinity of the Co complexes and on the catalytic activity are discussed in comparing with uncrowned analogues complexes.