Thomas Mathivet

Rhodium catalyzed hydroformylation of water insoluble olefins in the presence of chemically modified β-cyclodextrins: evidence for ligand-cyclodextrin interactions and effect of various parameters on the activity and the aldehydes selectivity

Abstract The biphasic rhodium catalyzed hydroformylation of water insoluble olefins in the presence of chemically modified β-cyclodextrins has been investigated. The influence of various parameters, such as the nature of the β-cyclodextrin, the concentrations of phosphine or cyclodextrin and the temperature is illustrated using 1-decene as a model substrate. The formation of inclusion complexes between the different components of the system is also discussed on the basis of NMR experiments. The results indicate that the chemically modified cyclodextrins (CyDs) must not be considered only as inverse phase transfer catalysts but also as compounds which, by trapping the water soluble ligand, can modify the equilibria between the different catalytic species.

Hydroformylation of higher olefins by rhodium/tris((1H, 1H, 2H, 2H-perfluorodecyl)phenyl)phosphites complexes in a fluorocarbon/hydrocarbon biphasic medium: effects of fluorinated groups on the activity and stability of the catalytic system

Abstract The synthesis of three fluorous triarylphosphites in which an ‘insulating’ ethylene segment separates the perfluoroalkylgroup from the aryl group is described. The stabilities, solubilities and partition coefficients of these new compounds are reported. The complexes generated in situ from these fluorous triarylphosphites and Rh(acac)(CO)2 have been tested as catalysts for the hydroformylation of various olefins under fluorous biphasic conditions. The activities and the selectivities were found to vary markedly with the position of the perfluoroalkylgroup on the aromatic ring. The possibility to recover the catalytic system was also investigated from consecutive recycling experiments.

UNEXPECTED SYNTHESIS OF A NEW HIGHLY FLUOROCARBON SOLUBLE PHOSPHITE FOR BIPHASIC CATALYSIS

Abstract The synthesis of tris(4-(1-oxoperfluorooctyl)-2-perfluorooctylphenyl)phosphite and tris(2,4-bis(perfluorooctyl)phenyl)phosphite from commercially available 1-iodoperfluorooctane and 2,4-dibromophenol is described. The stability and the solubility of these new compounds are reported.

Easy two-step synthesis of new tris(perfluoroalkylphenyl)phosphites

Abstract A general route for the synthesis of tris(perfluoroalkylphenyl)phosphites from halophenol derivatives and 1-iodoperfluorooctane is described. The stability and the solubility of these new compounds are reported.

Cationic borohydrido–neodymium complex: Synthesis, characterization and its application as an efficient pre-catalyst for isoprene polymerisation

The cationic borohydrido lanthanide complex [Nd(BH4)2(THF)5][B(C6F5)4]1, prepared from the reaction of Nd(BH4)3(THF)3 with [HNMe2Phl[B(C6F5)4], is highly active towards isoprene polymerisation upon activation with Al(i-Bu)3, whereas the in situ prepared ternary catalytic combination Nd(BH4)3(THF)3/[HNMe2Ph][B(C6F5)4]/Al(i-Bu)3, albeit less active, displays higher cis-selectivity and better control in terms of macromolecular data.