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DOI: 10.1055/s-0029-1217731
Highly Active and Magnetically Recoverable Pd-NHC Catalyst Immobilized on Fe3O4 Nanoparticle-Ionic Liquid Matrix for Suzuki Reaction in Water
Publication History
Publication Date:
27 August 2009 (online)
Abstract
Pd-NHC-ionic liquid matrix was immobilized into ionic liquid layers coated on the surface of Fe3O4. The immobilized Pd-NHC was used as a catalyst for Suzuki coupling. The catalyst exhibited both high catalytic activity and stability for the coupling between aryl bromide and arylboronic acid in water. This catalyst was simply recovered by an external permanent magnet and recycled without a significant loss in the catalytic activity.
Key words
heterogeneous catalysis - Suzuki reaction - palladium - magnetic nanoparticle - ionic liquids
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References and Notes
Surface Modification
of Nano-Fe
3
O
4
To a solution of 1-(3-trimethoxysilylpropyl)-3-methyl-imidazolium
chloride (0.28 g, 1.0 mmol) in toluene was added nano-sized Fe3O4 (Aldrich,
1.0 g). The mixture was stirred at 100 ˚C for
10 h. After cooling, the nano-Fe3O4 was magnetically
separated from reaction mixture. Modified Fe3O4 2 was washed with CH2Cl2 several
times and dried at 60 ˚C under vacuum. Elemental
analysis and weight gain showed that 0.67 mmol of 1-(3-trimethoxysilylpropyl)-3-methylimidazolium
chloride was anchored on 1.0 g of 2.
Immobilization
of NHC-Pd onto Modified Nano-Fe
3
O
4
2
To a solution of Pd-NHC 1 (195 mg, 0.29 mmol) and
1-butyl-3-methylimidazolium
hexafluorophosphate (165 mg, 0.58 mmol) in CH2Cl2 (2
mL) modified Fe3O4 2 (1.0
g) was added. The mixture was sonicated for 15 min at r.t., and then
CH2Cl2 was slowly removed under reduced pressure. The
resulting powder was washed with Et2O and dried under vacuum
at 60 ˚C to give Pd-NHC@Fe3O4-IL 3 (1.21 g). The Pd content of 0.17 mmol/g
was measured by inductively coupled plasma (ICP) analysis.
General Procedure
for the Suzuki Coupling Reaction
Aryl halide (1.0
mmol), arylboronic acid (1.2 mmol), K3PO4 (424
mg, 2.0 mmol), TBAB (161 mg, 0.5 mmol), dodecane (40 mg, internal
standard), and catalyst 3 (30 mg, 0.5 mol%) were
mixed in H2O (2.0 mL). The mixture was stirred at 75 ˚C
in an air atmosphere. The reaction was periodically monitored by
GC. After magnetic separation of the catalyst, the organic material
was twice extracted with Et2O. The organic phase was
dried over MgSO4, and the solvent was evaporated under
reduced pressure. The crude was analyzed by GC/GC-MS. The
product was purified by short column chromatography on silica gel.
Reuse of Pd-NHC@Fe 3 O 4 -IL 3 In the recycling experiment the reaction was performed by using a mixture of 4-bromoanisole (187 mg, 1.0 mmol), phenylboronic acid (134 mg, 1.2 mmol), K3PO4 (424 mg, 2.0 mmol), TBAB (161 mg, 0.5 mmol), and catalyst 3 (30 mg, 0.5 mol%) in H2O (2.0 mL) at 75 ˚C for 0.7 h. After completion of the reaction, the catalyst was magnetically separated from the solution. The solution was worked up as described above. The separated catalyst was successively reused for the next reaction without any pre-treatment.