With the aim at synthesizing novel allyl complexes that can potentially act as catalysts in the Tsuji–Trost catalyzed reaction, we have synthesized and characterized some allyl and 2-Meallyl palladium derivatives with one hemilabile bidentate or two strong mono-coordinating spectator ligands. The hemilabile ligands are constituted by one nitrogen heterocyclic carbene (NHC) fragment acting as the pivot bearing a labile wing with a pyridine nitrogen or sulfur atom as the second stabilizing atom. One of two monodentate ligands is in all cases PPh3 whereas the other is a mono- or partially coordinated hemilabile carbene. The complexes were characterized by standard spectroscopic methods and elemental analysis and in two cases by SC-XRD technique. The reactivity of two selected complexes toward the Tsuji–Trost reaction was tested by stoichiometric allyl amination carried out with piperidine and the results of such a mechanistic investigation integrated by a computational study are also reported in this paper.

Synthesis, characterization and a reactivity study of some allyl palladium complexes bearing bidentate hemi-labile carbene or mixed carbene/PPh3 ligands

SCATTOLIN, THOMAS;DE SANTO, CAROLINA;
2016-01-01

Abstract

With the aim at synthesizing novel allyl complexes that can potentially act as catalysts in the Tsuji–Trost catalyzed reaction, we have synthesized and characterized some allyl and 2-Meallyl palladium derivatives with one hemilabile bidentate or two strong mono-coordinating spectator ligands. The hemilabile ligands are constituted by one nitrogen heterocyclic carbene (NHC) fragment acting as the pivot bearing a labile wing with a pyridine nitrogen or sulfur atom as the second stabilizing atom. One of two monodentate ligands is in all cases PPh3 whereas the other is a mono- or partially coordinated hemilabile carbene. The complexes were characterized by standard spectroscopic methods and elemental analysis and in two cases by SC-XRD technique. The reactivity of two selected complexes toward the Tsuji–Trost reaction was tested by stoichiometric allyl amination carried out with piperidine and the results of such a mechanistic investigation integrated by a computational study are also reported in this paper.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11368/2897072
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