Dissociative pathway of the [Pd(2,2′-bipyridyl)(2-picoline)₂]²⁺ cation

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• 作者：Archimede Rotondo
• 关键词：EXSY NMR kinetics ; Square-planar complexes ; Dissociative mechanism
• 刊名：Inorganic Chemistry Communications
• 出版年：2010
• 出版时间：August 2010
• 年：2010
• 卷：13
• 期：8
• 页码：941-944
• 全文大小：438 K

文摘

Pyridines of C_s 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 Pd^II intermediate stabilized by γ-agostic interactions. Kinetic isotope effect, activation parameters, and crystal structure of the anti isomer support the D mechanism.