Title:Reusable MCM-41 Immobilized Rh(I) Hydroformylation Catalysts Built on Binaphthyl-based Phosphoramidite and Phosphite Ligands
VOLUME: 20 ISSUE: 13
Author(s):César A. Henriques, Fábio M. S. Rodrigues, Rui M. B. Carrilho, Mónica Silva, Auguste Fernandes, M. Filipa Ribeiro and Mariette M. Pereira
Affiliation:CQC, Department of Chemistry, University of Coimbra, Rua Larga, 3004-535 Coimbra, Portugal.
Keywords:Binaphthyl, phosphoramidite, phosphite, rhodium, covalent immobilization, MCM-41, supported catalyst, heterogeneous catalysis,
hydroformylation, FT-IR, N2-adsorption, thermogravimetry.
Abstract:The immobilization of Rh/phosphorus complexes in MCM-41 was performed using
two different methodologies. The first synthetic strategy was based on the covalent attachment of
a new binaphthyl-based phosphoramidite ligand through a trimethoxysilyl linkage, followed by
its complexation with the rhodium(I) precursor Rh(CO)2(acac). The resulting heterogeneized
Rh(I)/phosphoramidite complex was characterized by FT-IR, N2 adsorption and TG-DSC techniques,
which indicated its effective bonding to the mesoporous material. A second approach was
based on the physical adsorption of Rh(CO)2(acac) in MCM-41, followed by addition of tris[(R)-2'-(benzyloxy)-1,1'-binaphthyl-2-
yl]phosphite, to generate in situ a Rh(I)/phosphite complex, whose rhodium content was determined by chemical analysis (ICP). The two
hybrid materials were applied as catalysts in styrene hydroformylation, where both achieved high conversions and regioselectivity for the
branched aldehyde, under moderate reaction conditions. The covalent immobilization strategy allowed the reutilization of the
Rh/phosphoramidite catalyst, without loss of activity after four runs, while the physically adsorbed Rh/phosphite catalyst lost most of its
activity, with occurrence of rhodium leaching.
