Redox-Active Cobalt(II/III) Metal-Organic Framework for Selective Oxidation of Cyclohexene

被引：49
作者：
Zhang, Tao [1 ,2 ]
Hu, Yue-Qiao [1 ,2 ,3 ]
Han, Tian [1 ,2 ]
Zhai, Yuan-Qi [1 ,2 ]
Zheng, Yan-Zhen [1 ,2 ]
机构：
[1] Xi An Jiao Tong Univ, FIST, State Key Lab Mech Behav Mat, MOE Key Lab Nonequilibrium Synth Condensed Matter, 99 Yanxiang Rd, Xian 710054, Shaanxi, Peoples R China
[2] Xi An Jiao Tong Univ, Sch Sci, 99 Yanxiang Rd, Xian 710054, Shaanxi, Peoples R China
[3] Baoji Univ Arts & Sci, Coll Chem & Chem Engn, Key Lab Adv Mol Engn Mat, Baoji 721013, Peoples R China
来源：
ACS APPLIED MATERIALS & INTERFACES | 2018年 / 10卷 / 18期
关键词：
metal-organic framework; cobalt; catalysis; oxidation; cyclohexene; HETEROGENEOUS CATALYTIC-OXIDATION; COORDINATION POLYMERS; MAGNETIC-PROPERTIES; COPPER-COMPLEXES; ALKENES; CYCLOOCTENE; CHEMISTRY; CLUSTERS;
D O I：
10.1021/acsami.7b19323
中图分类号：
TB3 [工程材料学];
学科分类号：
0805 ; 080502 ;
摘要：
We report herein a new cobalt(II/III) mixed-valence metal-organic framework formulated as [(CoCo2III)-Co-II(mu(3)-O)(bdc)(3) (tpt)].guest 1, where bdc = benzene-1,4-dicarboxylate and tpt = 2,4,6-tri(4-pyridinyl)-1,3,5-triazine, which can be used as a redox-active heterogeneous catalyst for selective oxidation of cyclohexene on the allylic position without destroying the adjacent double bond. Two oxidants were chosen to demonstrate this result. For using tert-butyl hydroperoxide, the conversion rate is 63% and only allylic oxidation products (tert-butyl-2-cyclohexenyl-1-peroxide, 86%; 2-cydohexen-l-one, 14%) are found, whereas if using O-2 as oxidant, a total conversion of 38% is achieved and also only the allylic oxidation products (cyclohexenyl hydroperoxide, 72%; 2-cyclohexen-l-one, 20%; and cyclohex-2-en-l-ol, 8%) are found. The absence of any adduct on the double bond may be due to the unique radical chain mechanism triggered by the mixed-valent [(CoCo2III)-Co-II(mu(3)-O)] centers.
引用
收藏
页码：15786 / 15792
页数：7
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