Polymer-supported Pd(II) Wacker-type catalysts. II. Application in the oxidation of Dec-1-ene

Journal Article · Sun Aug 01 04:00:00 EDT 1993 · Journal of Catalysis; (United States)

DOI:https://doi.org/10.1006/jcat.1993.1229· OSTI ID:5719724

Tang, H G; Sherrington, D C ^[1]

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1. Univ. of Strathclyde, Glasgow (United Kingdom)

Seven polymer-supported Pd(II) catalysts have been prepared employing polymers carrying nitrile (cyanomethyl) ligands. Five of these involved polybenzimidazole backbones, one a polystyrene skeleton and the last a polyacrylonitrile backbone. The supported complexes have been used with CuCl[sub 2] co-catalyst to oxidize dec-1-ene primarily to methyl ketone under normal Wacker oxidation conditions. In some instances the supported complexes are more active than the (CH[sub 3]CN)[sub 2]PdCl[sub 2] model. The most active species is a highly rigid N-cyanomethylated polybenzimidazole and at least some of these metal centres may be coordinatively unsaturated. The effect of solvent, temperature, and co-catalyst ratio have been examined and discussed. The polymer-supported species remain very active at high temperature ([approximately]120[degrees]C) and require the addition of no hydrochloric acid to avoid irreversible precipitation of Pd(0) species. This is in complete contrast to homogeneous PdCl[sub 2], which is rapidly deactivated under similar conditions with copious Pd black formation. Pd(0) complexes immobilized on the polymer seem to be [open quotes]site isolated[close quotes] and unable to aggregate. Reoxidation therefore, remains facile. The polymer-supported species have been recycled seven times. An initial fall in activity levels takes place after three cycles and thereafter they remain essentially constant. Appreciable Pd leaching also occurs in the first reaction but is rapidly arrested. After [approximately]6 cycles Pd loss is only [approximately]1 ppm per cycle. Following the use of CuCl[sub 2] co-catalyst in the first cycle, no additional Cu(II) needs to be added; sufficient co-catalyst appears to be carried through with the isolated polymer-supported Pd(II) species.

• OSTI ID: 5719724
• Journal Information: Journal of Catalysis; (United States), Journal Name: Journal of Catalysis; (United States) Vol. 142:2; ISSN 0021-9517; ISSN JCTLA5
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKENES
CATALYSIS
CATALYST SUPPORTS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTIONS
CHLORIDES
CHLORINE COMPOUNDS
COMPLEXES
COPPER CHLORIDES
COPPER COMPOUNDS
COPPER HALIDES
HALIDES
HALOGEN COMPOUNDS
HETEROGENEOUS CATALYSIS
HYDROCARBONS
LIGANDS
MATERIALS
ORGANIC COMPOUNDS
ORGANIC POLYMERS
OXIDATION
PALLADIUM COMPLEXES
PETROCHEMICALS
PETROLEUM PRODUCTS
PLASTICS
POLYMERS
POLYOLEFINS
POLYSTYRENE
POLYVINYLS
SYNTHETIC MATERIALS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS