Chiral manganese(III) salen catalysts immobilized on MCM-41 and delaminated zeolites ITQ-2 and ITQ-6 through new axial coordinating linkers

被引:64
作者
Domínguez, I [1 ]
Fornés, V [1 ]
Sabater, MJ [1 ]
机构
[1] Univ Politecn Valencia, Inst Tecnol Quim UPV, CSIC, Valencia 46022, Spain
关键词
manganese; salen; asymmetric epoxidation; delaminated zeolites;
D O I
10.1016/j.jcat.2004.08.021
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
We report that the catalytic behavior and enantioselectivity of three different chiral Mn(III) salen complexes anchored to traditional supports such as MCM-41 (38-Angstrom pore diameter) and delaminated zeolitic materials ITQ-2 and ITQ-6 strongly depend on whether the complexes are attached to the surfaces through the chiral equatorial tetradentate salen ligand or via the apical ligand. As for the case of unsupported complexes, this experimental observation has been accounted for strong variations in the conformational preference of the catalyst intermediate toward the approaching olefin, as well as to unfavorable structural changes in the complex. In addition, control of the hydrophobicity of the surface allows for optimization of selectivity in obtaining chiral epoxides. (C) 2004 Elsevier Inc. All rights reserved.
引用
收藏
页码:92 / 99
页数:8
相关论文
共 31 条
[1]   A NEW FAMILY OF MESOPOROUS MOLECULAR-SIEVES PREPARED WITH LIQUID-CRYSTAL TEMPLATES [J].
BECK, JS ;
VARTULI, JC ;
ROTH, WJ ;
LEONOWICZ, ME ;
KRESGE, CT ;
SCHMITT, KD ;
CHU, CTW ;
OLSON, DH ;
SHEPPARD, EW ;
MCCULLEN, SB ;
HIGGINS, JB ;
SCHLENKER, JL .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (27) :10834-10843
[2]   Heterogeneous enantioselective epoxidation of olefins catalysed by unsymmetrical (salen) Mn(III) complexes supported on amorphous or MCM-41 silica through a new triazine-based linker [J].
Bigi, F ;
Moroni, L ;
Maggi, R ;
Sartori, G .
CHEMICAL COMMUNICATIONS, 2002, (07) :716-717
[3]   Utilisation of homogeneous and supported chiral metal(salen) complexes in asymmetric catalysis [J].
Canali, L ;
Sherrington, DC .
CHEMICAL SOCIETY REVIEWS, 1999, 28 (02) :85-93
[4]   COMPUTER MODELING OF SILICATES [J].
CATLOW, CRA ;
CORMACK, AN .
INTERNATIONAL REVIEWS IN PHYSICAL CHEMISTRY, 1987, 6 (03) :227-250
[5]   Silica gel anchored chiral Mn(III)salen complexes for enantioselective epoxidation of unfunctionalised olefins [J].
Choudary, BM ;
Chowdari, NS ;
Kantam, ML ;
Santhi, PL .
CATALYSIS LETTERS, 2001, 76 (3-4) :213-218
[6]   Chiral copper(II) bisoxazoline covalently anchored to silica and mesoporous MCM-41 as a heterogeneous catalyst for the enantioselective Friedel-Crafts hydroxyalkylation [J].
Corma, A ;
García, H ;
Moussaif, A ;
Sabater, MJ ;
Zniber, R ;
Redouane, A .
CHEMICAL COMMUNICATIONS, 2002, (10) :1058-1059
[7]   Strategies to improve the epoxidation activity and selectivity of Ti-MCM-41 [J].
Corma, A ;
Domine, M ;
Gaona, JA ;
Jordá, JL ;
Navarro, MT ;
Rey, F ;
Pérez-Pariente, J ;
Tsuji, J ;
McCulloch, B ;
Nemeth, LT .
CHEMICAL COMMUNICATIONS, 1998, (20) :2211-2212
[8]   Delaminated zeolite precursors as selective acidic catalysts [J].
Corma, A ;
Fornes, V ;
Pergher, SB ;
Maesen, TLM ;
Buglass, JG .
NATURE, 1998, 396 (6709) :353-356
[9]   New aluminosilicate and titanosilicate delaminated materials active for acid catalysis, and oxidation reactions using H2O2 [J].
Corma, A ;
Diaz, U ;
Domine, ME ;
Fornés, V .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (12) :2804-2809
[10]  
CORMA A, 1998, Patent No. 9717290