Benzylic oxidation with H2O2 catalyzed by Mn complexes of N,N′,N"-trimethyl-1,4,7-triazacyclononane:: spectroscopic investigations of the active Mn species

被引:44
作者
Bennur, TH [1 ]
Sabne, S [1 ]
Deshpande, SS [1 ]
Srinivas, D [1 ]
Sivasanker, S [1 ]
机构
[1] Natl Chem Lab, Catalysis Div, Pune 411008, Maharashtra, India
关键词
manganese complexes; Mn-tmtacn; selective oxidation; benzylic oxidation; oxidation with H2O2; ESR; spectroscopic investigations;
D O I
10.1016/S1381-1169(02)00132-2
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Mn complexes of N,N',N"-trimethyl-1,4,7-triazacyclononane (Mn-tmtacn) exhibit good catalytic activity, at ambient temperatures, for the benzylic oxidation of aromatics selectively to the corresponding alcohol and carbonyl compounds with H2O2 as oxidant in the presence of carboxylate buffers. The active Mn species in the reaction medium was investigated by UV-visible (UV-Vis), FT-IR-attenuated total reflectance (FT-IR-ATR) and electron spin resonance (ESR) spectroscopic techniques. The studies revealed the formation of terminal oxo- and mu-oxo-Mn(IV)-tmtacn complexes during the reaction. The oxo-manganese complexes and the nature of the carboxylic acid play an important role in the activation of the benzylic C-H bond. (C) 2002 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:71 / 80
页数:10
相关论文
共 26 条
[1]  
[Anonymous], 2014, SCIENCE
[2]   Mn-trimethyltriazacyclononane/ascorbic acid: a remarkably efficient catalyst for the epoxidation of olefins and the oxidation of alcohols with hydrogen peroxide [J].
Berkessel, A ;
Sklorz, CA .
TETRAHEDRON LETTERS, 1999, 40 (45) :7965-7968
[3]   BIOINORGANIC MODEL COMPLEXES FOR THE ACTIVE-SITE IN MANGANESE CONTAINING CATALASES - THE CRYSTAL-STRUCTURES OF [L2MNII2(MU-OH)(MU-O2CCH3)2](PF6).CH3OH AND [L'2MNIII2(MU-O)(MU-O2CCH3)2](I3)I.H2O [J].
BOSSEK, U ;
WIEGHARDT, K ;
NUBER, B ;
WEISS, J .
INORGANICA CHIMICA ACTA, 1989, 165 (01) :123-129
[4]   CHROMIUM-PILLARED CLAY AS A CATALYST FOR BENZYLIC OXIDATION AND OXIDATIVE DEPROTECTION OF BENZYL ETHERS AND BENZYLAMINES - A SIMPLE AND CONVENIENT PROCEDURE [J].
CHOUDARY, BM ;
PRASAD, AD ;
BHUMA, V ;
SWAPNA, V .
JOURNAL OF ORGANIC CHEMISTRY, 1992, 57 (22) :5841-5844
[5]  
COLLINS TJ, 1990, J AM CHEM SOC, V112, P897
[6]   Epoxidation of terminal or electron-deficient olefins with H2O2, catalysed by Mn-trimethyltriazacyclonane complexes in the presence of an oxalate buffer [J].
De Vos, DE ;
Sels, BF ;
Reynaers, M ;
Rao, YVS ;
Jacobs, PA .
TETRAHEDRON LETTERS, 1998, 39 (20) :3221-3224
[7]  
De Vos DE, 1999, ANGEW CHEM INT EDIT, V38, P980, DOI 10.1002/(SICI)1521-3773(19990401)38:7<980::AID-ANIE980>3.0.CO
[8]  
2-W
[9]   Highly selective epoxidation of alkenes and styrenes with H2O2 and manganese complexes of the cyclic triamine 1,4,7-trimethyl-1,4,7-triazacyclononane [J].
DeVos, D ;
Bein, T .
CHEMICAL COMMUNICATIONS, 1996, (08) :917-918
[10]  
DEVOS DE, 1996, J ORGANOMET CHEM, V195, P520