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本文研究了在金属四苯基卟啉[Co(II)TPP,Fe(III)TPPCI,Mn(III)TPPCI,Zn(II)TPP,Cu(II)TPP.TPP=四苯基卟啉]存在下,用氧气氧化芳醛的过程.测定了反应体系的吸氧动力学曲线;观察了氧化过程中金属卟啉的可见光谱的变化;研究了底物、金属卟啉在反应体系中的浓度以及溶剂等因素对反应的影响.结果发现,除能可逆键合分子氧的Co(II)TPP外,不具此种功能的Fe(III)TPPCI和Mn(III)TPPCl也能加速芳醛的氧化反应.然而,它们的催化作用是在金属四苯基卟啉与反应过程中积累起来的过酸作用,卟啉环遭到破坏后观察到的,此时可能形成了某种新的催化活性中心.金属卟啉本身对反应起抑制作用,它只是表观上的催化剂,其催化作用看来不应归结为对分子氧的活化.
In this paper, we studied the existence of metal tetraphenylporphyrin [Co (II) TPP, Fe (III) TPPCI, Mn (III) TPPCI, Zn (II) TPP, Cu (II) TPP.TPP = tetraphenylporphyrin] , The oxidation process of aromatic aldehydes with oxygen was carried out. The kinetic curves of oxygen absorption of the reaction system were measured. The changes of the visible spectrum of metalloporphyrins during the oxidation process were observed. The concentrations of substrate and metalloporphyrin in the reaction system, Solvent and other factors on the reaction.The results showed that addition of Fe (III) TPPCI and Mn (III) TPPCl, which can not reversibly bond molecular oxygen to Co (II) TPP, can also accelerate the oxidation of aromatic aldehydes However, their catalytic effect is the peracid effect that accumulates during the reaction of the tetraphenylporphyrin with the metal, which is observed after the destruction of the porphyrin ring. At this point, some new catalytic centers may be formed. Metalloporphyrin itself has an inhibitory effect on the reaction, it is just an apparent catalyst, and its catalytic effect does not appear to be attributed to the activation of molecular oxygen.