[Cu(H2btec)(bipy)]∞: a novel metal organic framework (MOF) as heterogeneous catalyst for the oxidation of olefins

被引:122
作者
Brown, Kareen [1 ]
Zolezzi, Santiago [1 ]
Aguirre, Pedro [1 ]
Venegas-Yazigi, Diego [2 ,3 ]
Paredes-Garcia, Veronica [2 ,4 ]
Baggio, Ricardo [5 ]
Novak, Miguel A. [6 ]
Spodine, Evgenia [1 ,2 ]
机构
[1] Univ Chile, Dept Quim Inorgan & Analit, Fac Ciencias Quim & Farmaceut, Santiago 1007, Chile
[2] Univ Chile, Ctr Invest Interdisciplinaria Avanzada Ciencias M, Santiago 1007, Chile
[3] Univ Santiago Chile, Fac Quim & Biol, Santiago, Chile
[4] Univ Tecnol Metropolitana, Dept Quim, Santiago, Chile
[5] Comis Nacl Energia Atom, Dept Fis, RA-1429 Buenos Aires, DF, Argentina
[6] UFRJ, Inst Fis, Rio De Janeiro, Brazil
关键词
TERT-BUTYLHYDROPEROXIDE; COPPER(II) COMPLEXES; HYDROTHERMAL SYNTHESIS; BUTYL HYDROPEROXIDE; EFFICIENT CATALYSTS; MECHANISTIC ASPECTS; CRYSTAL-STRUCTURES; HYDROGEN-PEROXIDE; EPOXIDATION; CYCLOHEXENE;
D O I
10.1039/b810414j
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A new extended metal-organic framework [Cu(H(2)btec)(bipy)](infinity) (1) (H(4)btec=1,2,4,5-benzenetetracarboxylic acid; bipy= 2,2'-bipyridine) has been hydrothermally synthesized. Violet crystals are formed in a monoclinic system with a space group C2/c; a = 10.1810(18) angstrom, b = 14.4360(18) angstrom, c= 12.894(3) angstrom, beta= 112.94(3)degrees. In the title compound 1 each Cu(II) centre has a distorted square planar environment, completed by two N atoms from one bipy ligand and two O atoms belonging to two dihydrogen benzene-1,2,4,5-tetracarboxylate anions (H(2)btec(2-)). The {Cu(bipy)}(2+) moieties are bridged by H(2)btec(2-) anions to form an infinite one-dimensional coordination polymer with a zig-zag chain structure along the c axis. A double-chain structure is formed by hydrogen bonds between adjacent zig-zag chains. There are also p-p stacking interactions between the bipy ligands, with an average distance of 3.62 angstrom resulting in a two-dimensional network structure. Compound 1 was tested as a catalyst for the oxidation of cyclohexene and styrene, with tert-butyl hydroperoxide (TBHP) as oxidant. The catalytic activity (24 h and 75 degrees C) found for [Cu(H(2)btec)(bipy)](infinity) shows a high value for the conversion of cyclohexene (64.5%), and a lower one for styrene (23.7%). High turnover frequency (TOF) values for the epoxide products were observed, indicating that the catalyst synthesized in this work, not only has a high activity and selectivity for epoxidation reactions but is also very efficient.
引用
收藏
页码:1422 / 1427
页数:6
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