Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
10244812 | Journal of Catalysis | 2005 | 10 Pages |
Abstract
Michael reaction of β-ketoesters with vinylketones at room temperature under solvent-free condition is investigated with various Fe3+ catalysts, including FeCl3 â
 6H2O supported on various supports (Fe-mica, Fe-mont, Fe-SiO2, Fe-Al2O3, Fe-NaY) and homogeneous catalysts, FeCl3 â
 6H2O and Fe(NO3)3 â
 9H2O. Fe3+-exchanged fluorotetrasilicic mica (Fe-mica) shows highest activity. Fe-mica exhibits almost quantitative yields of Michael adducts, high turnover numbers (TON = 1000), and a low level of Fe leaching. After simple work-up procedures, Fe-mica can be recycled without a loss in activity. The relationship between catalytic activity and the catalyst structure determined by XRD, UV-vis, and Fe K-edge XANES/EXAFS is discussed in terms of the effect of clay support on the structure and reactivity of Fe3+ species. The Fe3+ cation, highly dispersed in the interlayer of clay (mica or mont) or on SiO2, is more active than the cluster-like Fe3+ oxide or hydroxide species in Fe-NaY and Fe-Al2O3. UV-vis and XAFS results for the catalysts treated with reactants suggest that, during the reaction, the FeCl2(O)4 octahedral species in FeCl3 â
 6H2O or those on Fe-SiO2 are converted to the β-diketonato complexes with two β-diketonato ligands, whereas in Fe-mica β-diketonato complexes with one β-diketonato ligand are formed. The formation of β-diketonato complexes results in a slight lowering of the Fe oxidation number from 3+, probably as a result of the electron donation from the β-diketonato ligand to Fe3+ as a Lewis acid site. The lower numbers of β-diketonato ligand coordinated with Fe3+ in Fe-mica should result in a larger coordination strength for β-diketonato ligand than that in Fe-SiO2, which was confirmed by acetylacetone-TPD. Thus, the central carbon atom of the β-diketonato ligand in Fe-mica is more reactive toward nucleophilic attack by the coordinated enone, leading to higher activity for the Michael reaction.
Keywords
Related Topics
Physical Sciences and Engineering
Chemical Engineering
Catalysis
Authors
Ken-ichi Shimizu, Masato Miyagi, Toshiki Kan-no, Tsuyoshi Hatamachi, Tatsuya Kodama, Yoshie Kitayama,