Titre: Metal-Ligand Cooperative catalysis with Indenediide Palladium and Platinum Pincer Complexes
Endroit : Pavillon J.-Armand Bombardier, salle 1035 à 11 h
Hôte : Frank Schaper
Cette conférence sera prononcée par la Professeure Blanca Martin-Vaca du laboratoire Hétérochimie Fondamentale et Appliquée de l'Université Toulouse III - Paul Sabatier.
Résumé: Since the pioneering work of Shvo and Noyori, impressive developments have been achieved in metal-ligand cooperative catalysis. Here, the ligands not only modulate the stereoelectronic properties of the metal but also participate directly in the catalytic process (exhibiting the so-called non-innocent character), and such metal-ligand cooperation enables to activate/form chemical bonds under mild conditions. Over the last two decades, spectacular progress has been achieved in metal-ligand cooperative catalysis using pincer complexes. In particular, Milstein discovered an original aromatization/dearomatization process in pyridine-based pincer complexes.1
Recently, we described original indenediide Pd(II) pincer complexes (see scheme) combining an electrophilic Pd center and an electron-rich ligand backbone.2 The non-innocent character of the indenediide ligand has further been applied in the catalytic intramolecular addition of carboxylic acids/amides to alkynes. The reaction occurs in the absence of external base, thanks to a metal-ligand cooperative mode of action.3 The lactones/lactams are obtained with high selectivity and the reaction is unprecedentedly broad in scope, in particular concerning large cycles (> 6 membered rings). The impact of the ligand modulation and variation of the metal center on the course of the reaction will also be discussed.
1. Gunanathan, C.; Milstein, D. Acc. Chem. Res. 2011, 44, 588 .2.(a) Oulié, P.; Nebra, N.; Saffon, N.; Maron, L.; Martin-Vaca, B.; Bourissou, D. J. Am. Chem. Soc. 2009, 131, 3493 3. (a) Nebra, N.; Monot, J.; Shaw, R.; Martin–Vaca, B.; Bourissou, D. ACS Catalysis 2013, 3, 2930. (b) Espinosa-Jalapa, N. Á.; Ke, D.; Nebra, N.; Le Goanvic, L.; Mallet-Ladeira, S.; Monot, J.; Martin-Vaca, B.; Bourissou, D. ACS Catalysis 2014, 4, 3605. (c) Monot, J; Brunel, P; Kefalidis, C. E.; Espinosa-Jalapa, N. Á.; Maron,L. Martin-Vaca, B.; Bourissou, D. Chem. Sci. 2016,7, 2179.
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