title: Pyridylalkylamine ligands and their palladium complexes: structure and reactivity revisited by NMR.
abstract: Pyridylmethylamines or pma are versatile platforms for different catalytic transformations. Five pma-ligands and their respective Pd complexes have been studied by liquid state NMR. By comparing (1)H, (13)C and (15)N chemical shifts for each pma/pma-Pd couple, a general trend for the metallacycle atoms concerns variations of the electronic distribution at the pendant arm, especially at the nitrogen atom of the ligand. Moreover, the increase of the chemical shift of the pendant arm nitrogen atom from primary to tertiary amine is also related to the increase of crowding within the complex. This statement is in good agreement with X-ray data collected for several complexes. Catalytic results for the Suzuki-Miyaura reaction involving the pma-Pd complexes showed within this series that a sterically crowded and electron-rich ligand in the metallacycle was essential to reach the coupling product with a good selectivity. In this context, NMR study of chemical shifts of all active nuclei especially in the metallacycle could give a trend of reactivity in the studied family of pma-Pd complexes.
authors.affiliation: Université de Versailles Saint-Quentin-en-Yvelines, Institut Lavoisier de Versailles, UMR CNRS 8180, 45, avenue des Etats-Unis, 78035, Versailles, France.
authors.forename: Alexandre
authors.initials: A
authors.lastname: Requet
authors.forename: Olivier
authors.initials: O
authors.lastname: Colin
authors.forename: Flavien
authors.initials: F
authors.lastname: Bourdreux
authors.forename: Salim M
authors.initials: SM
authors.lastname: Salim
authors.forename: Sylvain
authors.initials: S
authors.lastname: Marque
authors.forename: Christine
authors.initials: C
authors.lastname: Thomassigny
authors.forename: Christine
authors.initials: C
authors.lastname: Greck
authors.forename: Jonathan
authors.initials: J
authors.lastname: Farjon
authors.forename: Damien
authors.initials: D
authors.lastname: Prim
keywords: 13C; 15N; 1H; N,N-bidentate ligands; N-heterocyclic benzhydrylamines; NMR; palladium; pyridylmethylamine