Cobalt(III)-oxo cubane clusters as catalysts for oxidation of organic substrates

被引:25
作者
Das, Birinchi Kumar [1 ]
Chakrabarty, Rajesh [1 ]
机构
[1] Gauhati Univ, Dept Chem, Gauhati 781014, India
关键词
Cobalt(III) cubane; aerobic oxidation; pinene epoxidation; alkylaromatic oxidation; homogeneous catalysis; ALPHA-PINENE; SELECTIVE OXIDATION; COMPLEXES; HYDROCARBONS; WATER; CORE; AUTOXIDATION; EPOXIDATION; CHEMICALS; ALCOHOLS;
D O I
10.1007/s12039-011-0111-6
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Transition metal coordination complexes play a vital role as catalysts in the oxidation of organic substrates including renewable chemicals in an economically viable and environmentally friendly way. Here we highlight the preparation, characterization and application of oxo-cubane complexes of cobalt(III) as oxidation catalysts using air and water as oxidants. Cobalt(III)-oxo complexes of the type Co(4)O(4)(O(2)CR)(4)L(4) have been prepared by a general method and these have been characterized by analytical, spectroscopic, electrochemical and crystallographic methods. These soluble complexes have shown promising utility as catalysts in the aerobic oxidation of side chains of alkylaromatic hydrocarbon compounds. Oxidation of neat ethylbenzene has shown very high conversion and selectivity for acetophenone formation. On the other hand, oxidation of p-xylene has been found to yield both p-toluic acid and terephthalic acid. It is also possible to oxidize p-xylene in an aqueous medium under moderate applied O(2) pressure. Selective epoxidation of alpha-pinene with air as the oxidant also takes place with the cobalt(III)-based homogeneous catalysts.
引用
收藏
页码:163 / 173
页数:11
相关论文
共 28 条
[1]   Tetranuclear cobalt(III) complex having the cubane Co4O4 core: Synthesis and structural analysis of the complex containing (2-Pyridylmethyl)glycine [J].
Ama, T ;
Okamoto, K ;
Yonemura, T ;
Kawaguchi, H ;
Takeuchi, A ;
Yasui, T .
CHEMISTRY LETTERS, 1997, (11) :1189-1190
[2]   The chemistry of cobalt acetate -: IV.: The isolation and crystal structure of the symmetric cubane, tetrakis[(μ-acetato)(μ3-oxo)(pyridine)cobalt(III)]•chloroform solvate, [Co4(μ3-O)4(μ-CH3CO2)4(C5H5N)4]•5CHCl3 and of the dicationic partial cubane, trimeric, [(μ-acetato)(acetato)tris(μ-hydroxy)(μ3-oxo)hexakispyridinetricobalt(III)]hexafluorophosphate•water solvate, [Co3(μ3-O)(μOH)3(μ-CH3CO2)(CH3CO2)(C5H5N)6][PF6]2•2H2O [J].
Beattie, JK ;
Hambley, TW ;
Klepetko, JA ;
Masters, AF ;
Turner, P .
POLYHEDRON, 1998, 17 (08) :1343-1354
[3]   Epoxidation of α-pinene catalysed by tetrameric cobalt(III) complexes [J].
Chakrabarty, R ;
Das, BK .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2004, 223 (1-2) :39-44
[4]  
CHAKRABARTY R, 2006, THESIS GAUHATI U ASS
[5]  
CHAKRABARTY R, 2004, CATALYSIS PETROLEUM, P287
[6]   Synthesis, structure, spectral and electrochemical properties, and catalytic use of cobalt(III)-Oxo cubane clusters [J].
Chakrabarty, Rajesh ;
Bora, Sanchay J. ;
Das, Birinchi K. .
INORGANIC CHEMISTRY, 2007, 46 (22) :9450-9462
[7]   Catalytic oxidation of p-xylene in water by cobalt(III) cubane cluster [J].
Chakrabarty, Rajesh ;
Kalita, Dipika ;
Das, Birinchi K. .
POLYHEDRON, 2007, 26 (06) :1239-1244
[8]   Enhanced selectivity in green catalytic epoxidation using a supported cobalt complex [J].
Chakrabarty, Rajesh ;
Das, Birinchi K. ;
Clark, James H. .
GREEN CHEMISTRY, 2007, 9 (08) :845-848
[9]   Catalytic Properties of Cobalt(III)-Oxo Cubanes in the TBHP Oxidation of Benzylic Alcohols [J].
Chakrabarty, Rajesh ;
Sarmah, Purabi ;
Saha, Bapan ;
Chakravorty, Stutee ;
Das, Birinchi K. .
INORGANIC CHEMISTRY, 2009, 48 (14) :6371-6379
[10]   Selective oxidation of para-xylene to terephthalic acid by μ3-oxo-bridged Co/Mn cluster complexes encapsulated in zeolite-Y [J].
Chavan, SA ;
Srinivas, D ;
Ratnasamy, P .
JOURNAL OF CATALYSIS, 2001, 204 (02) :409-419