有机铁配合物/NHPI催化氧化环己烷

为增强铁化合物协助N-羟基邻苯二甲酰亚胺（NHPI）催化氧化环己烷的效果，合成各种类型配体包括N、N，N、O和O、O配位式的有机铁配合物，铁与不同有机配体配位后增强了助催化能力，其中0.5 g四对氯苯基卟啉铁协助物质的量分数为10%的NHPI在100 ℃,氧压0.6 MPa,反应6 h，环己烷转化率46%。有机铁配合物在氧化过程中形成活性高价态铁中间体，将NHPI氧化为PINO自由基，提高了氧化性能，不同配体的助催化能力为N、N配位＞N、O配位＞O、O配位，这与高价铁活性中间体形成难易程度有关。

Catalytic oxidation of cyclohexane over organic iron complex/NHPI

To enhance the co catalytic effect of iron compounds for catalytic oxidation of cyclohexane over NHPI, different organic iron complexes involving N/N，N/O and O/O coordination were synthesized. Co catalytic capability of iron compounds were greatly improved after the coordination by different organic ligands. Cyclohexane conversion of 46% was obtained under the following condition: 100 ℃, O₂ pressure 0.6 MPa, reaction for 6 h over 10%(mol) NHPI and 0.5 g tetra (pchlor)phenylporphyrin iron(Ⅲ). During the oxidation process, the complex formed active high valence iron intermediate, which oxidized NHPI into PINO radicals and enhanced the oxidation capability. The co catalytic ability of different ligands declined in the following order: N/N＞N/O＞O/O coordination, which might be related to the likelihood for formation of active high valence iron intermediates.