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Zoekresultaten

Zoekopdracht: faculteit: "FNWI" en publicatiejaar: "2012"

AuteursR. Bellini, J.N.H. Reek
TitelCoordination studies on supramolecular chiral ligands and application in asymmetric hydroformylation
TijdschriftChemistry - A European Journal
Jaargang18
Jaar2012
Nummer23
Pagina's7091-7099
ISSN09476539
FaculteitFaculteit der Natuurwetenschappen, Wiskunde en Informatica
Instituut/afd.FNWI: Van 't Hoff Institute for Molecular Sciences (HIMS)
SamenvattingIn this study we introduce a series of monodentate pyridine-based ligands for which the phosphorus coordination mode to rhodium can be controlled by the binding of ZnII-templates to the pyridyl group. A series of monodentate phosphoroamidite and phosphite ligands have been prepared and studied under hydroformylation conditions by in situ high-pressure NMR and IR techniques. These studies reveal the exclusive formation of rhodium hydride complexes in which the phosphorus atom of the ligand resides in an axial position, trans to the hydride, but only after addition of ZnII-template. In the absence of these templates the usual mono-coordinated rhodium hydrido complexes are formed, with the phosphorus ligated in the equatorial plane, cis to the hydride. The catalytic performance of these complexes is evaluated in asymmetric hydroformylation of unfunctionalised internal alkenes in which the supramolecular change is reflected in higher activity and selectivity.
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