Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
1304292 | Inorganic Chemistry Communications | 2010 | 4 Pages |
Pyridines of Cs symmetry coordinated to [Pd(bipy)(pyr)2]2+ cations (bipy = 2,2′-bipyridyl; pyr = substituted pyridines) lead to syn and anti isomers due to their perpendicular orientation. Rate constants of syn–anti isomerizations of [Pd(bipy)(2pic)2]2+ (2pic = 2-methyl-pyridine) have been measured by quantitative 2D-EXSY NMR. Results suggest a dissociative (D) pathway involving an unsaturated 14-electrons PdII intermediate stabilized by γ-agostic interactions. Kinetic isotope effect, activation parameters, and crystal structure of the anti isomer support the D mechanism.
Graphical abstractPyridines of Cs symmetry in [Pd(bipy)(pyr)2]2+ cations (bipy = 2,2′-bipyridyl; pyr = substituted pyridine) lead to syn and anti isomers due to their perpendicular orientation. Rate constants of syn–anti isomerizations of [Pd(bipy)(2pic)2]2+ (2pic = 2-methyl-pyridine) have been measured by quantitative 2D-EXSY NMR. Results suggest a dissociative (D) pathway involving an unsaturated 14-electrons PdII intermediate. Kinetic isotope effect, activation parameters and crystal structure of the anti isomer support D mechanism.Figure optionsDownload full-size imageDownload as PowerPoint slide