کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1304292 | 974814 | 2010 | 4 صفحه PDF | دانلود رایگان |
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.
Pyridines 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 as PowerPoint slide
Journal: Inorganic Chemistry Communications - Volume 13, Issue 8, August 2010, Pages 941–944