Novel chromium (III) complexes with N4-donor ligands as catalysts for the coupling of CO2 and epoxides in supercritical CO2

10.1016/j.molcata.2013.10.021New neutral and cationic chromium(III) complexes with N4 Schiff base ligands have been prepared and characterized. These complexes are active catalysts for the cycloaddition of CO2 and styrene oxide in CH2Cl2 solutions, affording epoxide conversions in a 39¿92% range, with encouraging cyclic carbonate yields (up to 63%). It is to notice that the cationic species were significantly more active than their neutral analogs. Addition of tetrabutylammonium halides improved the selectivity toward styrene carbonate (87% yield). Dichloromethane could be avoided using solvent free or supercritical carbon dioxide as a solvent (scCO2) and, moreover, this improved the catalytic activity of the cationic complexes (TOF up to 652 h-1). Using scCO2, these chromium catalysts afforded the rapid and selective formation of cyclic carbonates from the coupling of CO2 to various linear terminal epoxides, such as epichlorydrin, propylene oxide and long chain terminal oxiranes. Coupling of cyclohexene oxide and carbon dioxide led to mixtures of poly(cyclohexene) carbonate and cyclic carbonate depending on the conditions (pressure and co-catalyst/catalyst ratio). Poly(cyclohexene) carbonate was isolated with a productivity 388 g/g Cr. Selective formation of the cyclic cyclohexene carbonate was obtained working under scCO2 conditions

Rhodium-sulfonated diphosphine catalysts in aqueous hydroformylation of vinyl arenes: high-pressure NMR and IR studies

Hydroformylation of vinyl arenes (p-metboxystyrene and p-fluorostyrene) was performed in aqueous solutions using as catalyst precursor [Rh(mu-OMe)(cod)](2) (cod = 1,5-cyclooctadiene) associated with the sulfonated 1,3-diarylphosphines (tetra-sulfonated 1,3-bis(diphenylphosphino)propane (dpppts)) and the chiral (S,S)-bdppts (2,4-bis(diphenylphosphino)pentane). The influence of pH on the reaction rate was studied. After 24 h conversion was practically total with the achiral system in basic medium for the substituted styrene substrates. Selectivities in aldehydes were >85%. At neutral pH, the asymmetric hydroforrnylation of p-substituted styrenes using the rhodium-bdppts systems provides low conversion but the enantioselectivities were as high as 66%, the highest reported so far for this kind of substrates in aqueous systems. Comparison experiments using rhodium precursors with the non-sulfonated bdpp in organic solvents indicated that the enantioselectivity was higher in aqueous solutions for the p-methoxystyrene derivative and slightly lower for p-fluorostyrene. However, in both the cases the conversions in aqueous systems were low. High-pressure NMR and IR experiments in water/methanol indicate that [RhH(CO)(2)(sulfonated diphosphine)] species form under catalytic conditions in basic medium. At neutral pH, the main species observed in the case of the bdppts ligand is [Rh(bdppts)(2)](+) which may account for the low conversion in this medium. (C) 2002 Elsevier Science B.V. All rights reserved

Chromium complexes with tridentate NN'O Schiff base ligands as catalysts for the coupling of CO2 and epoxides

10.1016/j.molcata.2013.11.026New Cr(III) hexacoordinated complexes with tridentate NN'O-donor Schiff base ligands, M(NN'O)2Cl, have been prepared. They form active catalytic systems for the coupling of epoxides and carbon dioxide in the presence of co-catalysts. Best results were obtained with the complex with N-(2-pyridylmethyl)-3,5-di-tert-butyl-salicylaldimine (1) ligand and a co-catalyst. Cyclohexene oxide reacts with carbon dioxide in the presence of these catalysts to form mixtures of polycarbonate (PC) (productivity up to ca. 900 g PC/g Cr) and cyclic carbonate depending on the co-catalyst and conditions employed. Cyclopentene, styrene and propylene oxides form selectively the cyclic carbonates at the conditions studied (epoxide conversion up to 97%). Although some of the co-catalysts are also active for the cycloaddition, the presence of both complex and co-catalyst has proved to be beneficial

Chiral S,S-donor ligands in palladium-catalysed allylic alkylation

Chiral dithioether ligands have been tested in the model Pd-catalysed allylic alkylation reaction of (+/-)-3-acetoxy-1,3-diphenyl-1-propene with dimethyl malonate. giving high enantioselectivity (up to 81% e.e.) for the first time in this type of system. Pd(Il)-allylic intermediates, [Pd(eta (3)-1,3-Ph-2-C3H3)(dithioether)]PF6 were prepared and characterised both in solution by NMR spectroscopy and solid state. The X-ray structure for [Pd(eta (3)-1,3-Ph-2-C3H3)(L)]PF6 (L=(R,R)-7,8-O-isopropylidene-1,5-dithiacyclononane) was determined. (C) 2001 Elsevier Science Ltd. All rights reserved

Allylic alkylations catalyzed by palladium systems containing modular chiral dithioethers. A structural study of the allylic intermediates

Palladium allylic systems containing modular chiral dithioether ligands were chosen as catalysts for a systematic study of homodonor ligands in allylic alkylation reactions. For this purpose, new type-DMPS (4-6) and -DEGUS (8, 9) ligands were synthesized. Dithioethers 4-6 afforded high activities and excellent selectivities in all Pd-catalyzed allylic reactions. Particularly the Pd/6 catalytic system provided b-VIII with an ee > 99% and a regioselectivity 1/b (VIII) = 1/1.6. A family of intermediate complexes containing several allyl groups (symmetrical, 13-16 and 20, and nonsymmetrical, 17-19, moieties) and dithioether ligands (4-6, 8, 9, 11, and 12) is described. The complexes were fully characterized both in solution and in the solid state. X-ray structures of four of these complexes (16-18 and 20) were determined. The diastereomers present in solution were studied by NMR spectroscopy, and in some cases it was possible to establish a relationship between the diastereomeric excesses and the selectivities found in the catalytic process