74888-93-0Relevant articles and documents
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Holzhey, Nancy,Pitter, Stephan,Dinjus, Eckhard
, p. 243 - 248 (1997)
Immobilized catalysts prepared from [Pd(η5-C5H5)(η3-C3H5)] (5) and polymer bound phosphines 4a-c are used to catalyse C,C coupling reactions of carbon dioxide and any organic co-substrate for the first time in a heterogeneous way. These phosphines, synthesised from chloromethylated polystyrene, are characterised by their elemental analysis data and NMR spectra. The immobilized catalyst from polymer 4a and 5 catalyses the formation of the δ-lactone 2-ethylidene-6-heptene-5-olid (1). With low reaction rates, up to 72% selectivity to 1 is observed. These catalysts can be used in multiple reactions. In an analogous procedure using polymer 4b, the synthesis of C17 carboxylic esters is successful.
Bidentate ferrocenylphosphines and their palladium(II)dichloride complexes - X-ray structural and NMR spectroscopic investigations and first results of their characteristics in the Pd-catalysed cooligomerisation of 1,3-butadiene with CO2
Elsagir, Anja R.,Ga?ner, Franz,G?rls, Helmar,Dinjus, Eckhard
, p. 139 - 145 (2007/10/03)
The chiral 1,1′-bis(di(+)-menthylphosphino)ferrocene (dmenpf, 1b) and achiral 1,1′-bis(diisopropylphosphino)ferrocene (disoppf, 1a) were prepared from the corresponding tertiary chlorophosphines 2b and 2a and the dilithiated ferrocene-TMEDA complex as analytically pure crystals. The synclinic eclipsed conformation of the Cp rings and the Cp(1)-Fe-Cp(1)′ angle in 1b was determined to be 175.0(2)° by X-ray structure analysis. With H2[PdCl4] 1a forms the bimetallic complex (disoppf)PdCl2 (3a). In contrast to the structure of the free ligand disoppf (1a), the X-ray structure of 3a and the NMR spectra in solution as well as in the solid state show that the P atoms are chemically and magnetically equivalent. The conformation of the Cp rings converts from an eclipsed to a staggered conformation. The ferrocene-based ligands show significant activity in the Pd-catalysed cooligomerisation of 1,3-butadiene with CO2
PALLADIUM- AND RHODIUM-CATALYZED SYNTHESIS OF ESTERS BY REACTION OF BUTADIENE, CARBON DIOXIDE, AND OXIRANES
Behr, Arno,Kanne, Ulrich
, p. 215 - 224 (2007/10/02)
Butadiene, carbon dioxide and ethylene oxide interact in the presence of palladium or rhodium catalysts to give (2'-hydroxyethyl)2-ethylidene-4,6-heptadienoate in a "one pot" reaction.When propylene oxide was used, two related isomeric esters with an additional methyl group in the alcohol part of the ester were obtained, in yields of up to 24percent.Kinetic investigations suggest that the reaction occurs via the lactone 2-ethylidene-6-hepten-5-olide.The products are accounted for in terms of a mechanism involving the coordination of the oxirane to an allylic transition metal carboxylate complex and insertion of the oxirane to give an allylic alkoxy complex.Elimination of the products occurs via a hydrogen migration step.