五氨釕(III)N-甲基??錯合物與鄰苯二酚衍生物之還原反應動力學探討

THUIR > College of Science > Department of Chemistry > Theses and Dissertations > Item 310901/2542

Please use this identifier to cite or link to this item: http://140.128.103.80:8080/handle/310901/2542

Title:	五氨釕(III)N-甲基??錯合物與鄰苯二酚衍生物之還原反應動力學探討
Other Titles:	The Reduction Reactions of Catechol Derivatives by N- Methylpyrazinium Complex of Pentaammineruthenium(III)
Authors:	陳愉宜 Chen, Yu-Yi
Contributors:	葉玉堂 Yeh, Andrew 東海大學化學系
Keywords:	臨苯二酚;類黃酮;氧化還原 catechol;flavonoid;electron transfer
Date:	2006
Issue Date:	2011-03-21T06:33:03Z (UTC)
Abstract:	[RuIII(NH3)5pzCH3]4+錯合物氧化維他命C及一系列catechols之反應，屬外圈電子轉移機構，在[H+] = 0.01 – 0.1M，μ = 1 M HClO4 / LiClO4 , T=25℃條件下進行動力學探討，結果分別得k0 = (4.9±0.3) × 102 (Ascorbic acid)，(5.88± 0.04) × 102 (Pyrocatechol)，(6.31± 0.03) × 102 (catechin) ; k1 = (2.78± 0.01) × 107 (ascorbic acid)，(1.32± 0.04)× 1010 (Pyrocatechol)，(1.01± 0.01) × 107 (4-nitrocatechol)，(4.68± 0.04) × 109 (catechin) 。動力學結果顯示hydroquinones與ascorbic acid反應機構相似，修正反應能障kcorr = 後，我們發現catechols反應活性比ascorbic acid大了ㄧ次冪，因此catechols的抗氧化力比ascorbic acid好。Marcus 理論修正，進一步發現catechols kex應較ascorbic acid大2次冪以上。 The oxidation of ascorbic acid and a series of catechols (hydroquinones) by [RuIII(NH3)5pzCH3]4+ complexes undergoes an outer-sphere electron transfer mechanism. The kinetic studies of the reaction at [H+] = 0.01 – 0.1M specific rate constants of reaction at k0 = (4.9±0.3) × 102 (ascorbic acid)，(5.88± 0.04) × 102 (pyrocatechol)，(6.31± 0.03) × 102 (catechin) ; k1 = (2.78± 0.01) × 107 (ascorbic acid)，(1.32± 0.04)× 1010 (pyrocatechol)，(1.01± 0.01) × 107 (4-nitrocatechol)，(4.68± 0.04) × 109 (catechin), respectively at μ = 1 M HClO4 / LiClO4 and T = 25°C. The reactivities of the catechols were found to be greater than that of the ascorbic acid after the correction of the specific rate constants by the contribution of equilibrium barrier. This implies that the self-exchange rate constants of the catechols are grater than that of the ascorbic acid according to Marcus theory predictive.
Appears in Collections:	[Department of Chemistry ] Theses and Dissertations

Files in This Item:

File	Size	Format
095THU00065002-001.PDF	71Kb	Adobe PDF	237	View/Open
095THU00065002-002.PDF	149Kb	Adobe PDF	259	View/Open
095THU00065002-003.PDF	812Kb	Adobe PDF	1368	View/Open

Loading...