Supramolecular bidentate phosphorus ligands based on bis-zinc(II) and bis-tin(IV) porphyrin building blocks |
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Authors: | Slagt Vincent F van Leeuwen Piet W N M Reek Joost N H |
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Institution: | van 't Hoff Institute of Molecular Sciences, University of Amsterdam, Nieuwe Achtergracht 166, 1018 WV, Amsterdam, The Netherlands. |
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Abstract: | Selective metal-ligand interactions have been used to prepare supramolecular bidentate ligands by mixing monodentate ligands with a suitable template. For these assemblies pyridine phosphorus ligands and a zinc(II) porphyrin dimer were used. In the rhodium-catalysed hydroformylation of 1-octene and styrene improved selectivities have been obtained for some of the assembled bidentate ligand systems. In the palladium catalysed asymmetric allylic alkylation similar effects were observed; the enantioselectivity increased by using a bisporphyrin template. The preparation of supramolecular catalyst systems was also explored using tin-oxygen interactions. Dihydroxotin(IV) porphyrin and carboxylic phosphorus ligands assemble into supramolecular ligands and the phosphorus donor atom coordinates to transition metals. The stronger oxygen-tin bond, compared to pyridine-zinc does not result in a better performance of the catalyst. |
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