- 作者: 黃文樞
- 作者服務機構: 國立中山大學化學系
- 中文摘要: 本研究探討了在雙甲基鈷(三價)錯化物,MeCo (TIM)及MeCo(bipy)之陽極氧化的循環電位中,電子轉移之不可逆性的定性及定量上之準繩。此二錯化物經電子轉移所形成的不安定性中間活性體,導致了選擇性地斷裂一個甲基配位。乙烷之生成反應機構,如分別代表MeCo (TIM)及MeCo(bipy)之氧化裂鍵反應的圖表C及圖表D所示,符合於乙烷對甲烷之相對生成量對此下三種實驗參數的相依性:(1)雙甲基鈷(三價)錯化物之濃度,(2)外加電流量,及(3)化學攫取物之濃度。此二反應機構之不同乃由於導致乙烷生成之活性前置物之不同,此可由對鹵基之選擇性及對離子強度效應之探討予以證實之。
- 英文摘要: Qualitative as well as quantitative criteria for irreversibility of electron-transfer in cyclic voltammetryof trans-Me CO(TIM)CIO and cis-Me Co(bipy) Cl are studied. The metastable transient intermediatesresulting from the irreversible electron-transfer of these two complexes lead to the selective scission of onlyone methyl ligand. Mechanisms of the ethane formation presented as Scheme C and Scheme D for MeCo-(TIM) and Me Co(bipy), respectively, are consisent with the dependence of the relative yield of ethaneon the following experimental parameters:(1)the concentration of the dimethylcobalt(III) complexes,(2) the applied current, and (3) the concentration of the chemical traps. The difference in mechanisticfate between these two complexes is attributed to the difference in the active precursor which leads to theethane formation, and is verified by halogen selectivity and ionic strength effect studies.
- 中文關鍵字: --
- 英文關鍵字: --