Ru(Ⅲ) : 거대고리 착물의 합성과 이를 촉매제로 이용한 올레핀의 산화반응 Macrocyclic Complexes and Catalytic Oxidation of Olefins = Synthesis of Ruthenium(Ⅲ)

다국어 초록 (Multilingual Abstract)

The complexes were prepared by the controlled dropwise addition method . Reactions of K_2[RuCl_2·H_2O] with cyclam, meso, and rac (cyclam=1,4,8,11- tetraazacyclotetradecane, meso =C-meso-5, 7, 7, 12, 14, 14-hexamethyl-1,4,8,11-tetraazacyclotrtradecane, rac=C-rac-5, 7, 7,12, 14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) in ethanol yielded trans-[RuLCl_2]Cl (L= cyclam, meso, rac) complexes.
The ligand-to-metal charge-transfer transition in the UV vis spectrum of trans-[Ru(meso)Cl_2] Cl determined at 20℃ has been appeared at 370nm and 314㎚, while the spectrum for trans-[Ru(cyclam)Cl_2]Cl complex is considerably red-shifted.
Oxidation of olefins using trans-[RuLCl_2]Cl complexes as catalyst was investigated in dichloroethane, in with sodium hypocholrite, hydrogen peroxide and tert-butyloxide were used as terminal oxidant and olefins were styrene,cyclohexene, 1-hexene, cyclooctene, and 1-octene. In this experimental condition, sodium hypochlorite was rather efficient terminal oxidant than hydrogen peroxide and tert-butylperoxide. In addition trans-[Ru(meso)Cl_2]Cl complex was rather efficient catalyst than trans-[Ru(cyclam) Cl_2]Cl complex, when sodium hypocholrite was used as terminal oxidant.