六氟乙醯丙酮及雙氮秦配位基錳錯化合物對過氧化氫不均化催化反應之活性與動力學研究

洪當明

慈濟技術學院護理科

摘　　要

　　雙核〔Mn2(hfac)4(pyz)(H2O)2 2H2O〕(1)和單核〔Mn(hfac)2(pym)(H2O)〕(2)兩個錳錯化合物對過氧化氫的分解成氧氣和水，非常有效率的催化作用。由錯化合物分解過氧化氫反應的氧氣釋出結果，證明此兩錯化合物對於過氧化氫在砒碇中不均化分解具有催化的活性。兩錯化合物催化活性的更換值分別為每秒 0.215 及 0.119 ，顯示錯化合物(1)的活性比錯化合物(2)的活性強。

錯化合物催化過氧化氫分解的反應速率定律式為：－ｄ〔H2O2〕dt＝ｋ〔H2O 2〕x〔complex〕y ，指數ｘ、ｙ分別代表過氧化氫、錯化合物的反應級數，ｋ為反應速率常數。實驗結果：錯化合物(1)之ｘ、ｙ和ｋ值分別為1.0192、1.0005和2.6405升莫耳．秒；錯化合物(2) 之ｘ、ｙ和ｋ值分別為0.9884、1.0069和2.1959升莫耳．秒。

錯化合物催化過氧化氫分解的最大速率(Vmax)和米氏常數(Km)實驗結果為：錯化合物(1)之Vmax和Km值分別為0.1087mM/sec和0.1256M；錯化合物(2)之Vmax和Km值分別為13.1mM/sec和18.83M。







Kinetic Studies and Catalytic Activity for H2O2 Disproportionation Of Bis（1,1,1,5,5,5- hexafluoropentane-2,4-dionate）mamganese（II）Complexes with Diazine Ligands



Dang-Ming Hong

Department of Nursing

Tzu Chi College of Technology

Abstract

　　 Binuclear complex 〔Mn2（hfac）4（pyz）（HO2）2. 2HO2〕 (1)and mononuclear complex 〔Mn（hfac）2（pym）（H2O）〕 (2)（hfac=1,1,1,5,5,5-hexafluoropentane-2, 4-dionate, pyz=pyrazine and pym=pyrimidine） catalyze hydrogen peroxide decomposing to dioxygen and water very efficiently. The evolution of O2 by decomposing of H2O2 shows that all the complexes are catalytic activity towards disproportionation of H2O2 in pyridine at 10℃. The turnover number of complex 1, 2 are 0.215 sec-1, 0.119 sec-1, respectively, reveals that the complex 1 is more active than that of complex 2.

The decomposition of H2O 2 by complex 1 and 2 has reaction rate law of the form - d〔H2O2〕dt =ｋ〔H2O 2〕X〔complex〕Y, the exponents x, y represent the order of the reaction and K is rate constant. The values of x, y and k are obtained as 1.0192, 1.0005 and 2.6405 dm3 mol-1 sec-1 for complex 1; 0.9884, 1.0069 and 2.1959 dm3 mol-1 sec-1 for complex 2, respectively.

The maximal rate, Vmax, of the catalase-like reaction is 0.1087 mM/sec　per mg for complex 1, 13.1 mM/sec per mg for complex 2. The Michaelis-Menten constant, Km, of complex 1, 2 are 0.1256 M and 18.83 M for hydrogen peroxide.

Keywords： disproportionation; turnover number; Michaeli