Oxidative addition of allyl and propargyl halides on palladium(0) complexes bearing bidentate ligands with quinolinic structure

•Novel Pd(0) complexes of dimethylfumarate and bidentate quinoline derived ligands were synthesized.•The Pd(0) derivatives were reacted with allyl and propargyl halides and the reaction products characterized.•The solid state structures of one starting complex and two product of oxidative addition were resolved.•A mechanism for the oxidative addition was proposed.

We have synthesized three Pd(0) complexes stabilized by the olefin dimethyl fumarate and bidentate ligands based on the quinoline frame with thioetheric or diphenylphosphine function. We have reacted all the synthesized complexes with allyl or propargyl halides and isolated the products of the resulting oxidative addition. The solid state structures in the case of a Pd(0) derivative 1C and of the allenyl complexes 2Af and 2Ag have been resolved and we performed some computational calculations in order to establish whether the formation of allenyl or propargyl derivative as reaction products could be influenced by their reciprocal thermodynamic stability or by kinetic reasons. In this respect we have also carried out some kinetic investigations and hypothesized a plausible mechanism of the oxidative addition.

Graphical abstractThree Pd(0) complexes bearing the olefin dimethylfumarate and bidentate ligands based on the quinoline frame were synthesized, characterized and reacted with allyl and propargyl halides. The solid state structures of one starting complex and of two reaction products have been resolved and a kinetic study carried out.Figure optionsDownload full-size imageDownload as PowerPoint slide