八正丁硫基四氮杂金属卟啉的合成、表征及催化氧化苯甲醇性能研究

Synthesis,Characterization of Metalloporphyrazines with Octakis(Butylthio)and Their Catalytic Oxidation Performance for Benzyl Alcohol

成功合成了4种不同中心金属(Co、Mn、Fe和Ni)的八正丁硫基四氮杂卟啉配合物,即CoPz(SBu)8、MnPz(SBu)8、FePz(SBu)8、NiPz(SBu)8,通过1 HNMR、UV-Vis和MALDI-TOF-MS等对其结构进行了表征,并采用催化氧化苯甲醇评价其催化活性。结果表明,在以邻二甲苯为溶剂、氧气为氧化剂、反应温度为100°C、反应时间为12h、K2CO3为助剂的条件下,苯甲醇可被高选择性氧化为苯甲醛,且4种不同中心金属的八正丁硫基四氮杂卟啉配合物催化氧化苯甲醇的活性顺序为:MnPz(SBu)8>CoPz(SBu)8>FePz(SBu)8>NiPz(SBu)8,其中MnPz(SBu)8活性最好,转化率为84.7%,选择性>99%。八正丁硫基四氮杂金属卟啉的催化活性与其第一氧化峰电位密切相关。

Metalloporphyrazines with octakis（butylthio） （M = Co, Mn, Fe and Ni） were successfully synthe- sized and then characterized by 1HNMR,UV-Vis and MALDI-TOF-MS. The catalytic activities of metallopor phyrazines with octakis （butylthio） were evaluated by catalytic oxidation for benzyl alcohol. Results showed that, under the conditions of o-xylene as a solvent, oxygen as an oxidant, reaction temperature of 100 ℃, reaction time of 12 h and K2CO3 as an additive,benzyl alcohol could be highly selectively oxidized to benzaldehyde. The catalytic activities of metalloporphyrazines with octakis （butylthio） followed an order of MnPz（SBu）8 〉CoPz （SBu）8〉FePz（SBu）8〉NiPz（SBu）8. The highest conversion of benzyl alcohol was up to 84.7% by using MnPz （SBu）8 as the catalyst, and benzaldehyde was detected to be the only product with a selectivity above 99%. Their catalytic oxidation activities were closely related with the first oxidation peak potential.