有机铁配合物/NHPI催化氧化环己烷  

Catalytic oxidation of cyclohexane over organic iron complex/NHPI

作　　者：张延路[1,2] 赵文军[1] 范晓芸[1,2] 陈勇[1,2] 杨丹红[1,2] 高林[1] 

机构地区：[1]中国科学院新疆理化技术研究所,新疆乌鲁木齐830011 [2]中国科学院研究生院,北京100049

出　　处：《工业催化》2009年第4期45-49,共5页Industrial Catalysis

摘　　要：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6h,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。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-（p-chlor） 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.

关 键 词：催化化学 环已烷 NHPI 卟啉铁 席夫碱铁 EDTA铁 尿素铁 

分 类 号：O643.36[理学—物理化学] TQ426.94[理学—化学]