七(正丁硫基)-(正丁氧基)四氮杂金属卟啉活化分子氧催化氧化苯甲醇的性能研究

Oxidation of Benzyl Alcohol Catalyzed by Hepta(n-butylthio)-mono(n-butoxy) metalloporphyrazines Through Activating Molecular Oxygen

在合成卟啉衍生物七(正丁硫基)-(正丁氧基)四氮杂卟啉[H_2Pz(SBu)_7(OBu)]的基础上,进一步合成了它的金属配合物——含硫四氮杂金属卟啉[MPz(SBu)_7(OBu),M=Mn(Ⅱ)、Fe(Ⅲ)、Co(Ⅱ)、Ni(Ⅱ)],并通过UV-Vis、MALDI-TOF-MS对其进行了表征;以得到的4种金属配合物为催化剂,通过活化分子氧氧化苯甲醇的能力来评估其催化活性,并优化了催化氧化苯甲醇的反应条件。结果表明,4种金属配合物对苯甲醛均表现出极好的选择性(≥99%),其催化活性顺序为MnPz(SBu)_7(OBu)>CoPz(SBu)_7(OBu)>FePz(SBu)_7(OBu)>NiPz(SBu)_7(OBu),其中MnPz(SBu)_7(OBu)的催化活性最高,苯甲醇转化率达到84%,其次是CoPz(SBu)_7(OBu),转化率达到65%。

Based on preparation of porphyrazine derivatives hepta（n-butylthio）-mono（n-butoxy）pop phyrazine [H2Pz（SBu）7 （OBu）], the metal complexes [MPz （SBu）7 （OBu）, M = Mn（ Ⅱ ）, Fe（ Ⅲ ）, Co（ Ⅱ ）, Ni （ Ⅱ ）] were further synthesized and characterized by UV-Vis and MALDI-TOF-MS. And these complexes were used as catalysts,whose catalytic activities were assessed by activating molecular oxygen to oxidize benzyl alcohol. The catalytic oxidation conditions of henzyl alcohol were optimized. Results indicated that,four metal complexes showed excellent selectivity（≥99%） for benzaldehyde,and their catalytic activities followed an order of MnPz（SBu）7 （OBu） 〉CoPz（SBu）7 （OBu））FePz（SBu）7 （OBu）〉NiPz（ SBu）7 （OBu）, in which the catalytic activity of MnPz（SBu）7 （OBu） was the best with the benzyl alcohol conversion rate of 84%,the next was CoPz（SBu）7 （OBu） with the benzyl alcohol conversion rate of 65%.