Synthesis and Reactivity of Novel Alkylcobalt Macrocycles

• Main Authors: Da-dong Jian, 簡大棟
• Other Authors: Shao-Yung Lee
• Format: Others
• Language: zh-TW
• Online Access: http://ndltd.ncl.edu.tw/handle/21383494337722644984

碩士 === 義守大學 === 生物技術與化學工程研究所碩士班 === 95 === Alkylcobalt macrocycles are often used to investigate the cobalt-carbon bond energy owing to its similar structure with coenzyme B12. In this thesis the reaction of cobalt macrocyclic complex with alkyl hydroperoxide was used to synthesize RCo(tim)(H2O)(ClO4)2 (R=CH3，C2H5; tim = 2,3,9,l0-tetramethyl-1,4,8,11- tetraazacyclotetradeca-1,3,8,10-tetrane). The complex of C2H5Co(tim)(H2O)(ClO4)2 crystallizes in the monoclinic space group P21/c with Z = 4. The unit cell dimensions are a = 11.8752 (11) Å, b = 15.0797 (14) Å, c = 13.4884 (12) Å, β= 98.845(2)° and V= 2386.7(4) Å3. The reduction reaction of organocobalt complex with Cr2+ ion were studied under pseudo-first-order condition and the rate law was determined as: Rate = k[RCo(tim)(H2O)2+][ Cr2+] (R=CH3，C2H5) The thermal activation parameters(ΔH‡、ΔS‡) were also determined. The influence of the size of the alkyl group on the cobalt, the structure of the ligand for this reaction was discusse.