−25 °C. Kinetic studies revealed lutidine-catalyzed and noncatalyzed isomerization pathways. The lutidine-catalyzed pathway involves five-coordinate (PO-OMe)PdMe(lut)2 intermediates that undergo Berry pseudorotation. Kinetic studies, structure–activity relationships, solvent effects, and density functional theory calculations for the noncatalyzed pathway are most consistent with a mechanism, originally
研究了(PO-OMe)P
DMe(lut)([PO-OMe] - = 2- P(2-OMe-Ph)2 } -4-Me-
苯磺酸盐)的顺式/反式异构化(邻-膦基-
芳烃磺酸盐)PdR(
乙烯)物质在
乙烯聚合中的链增长反应。的非平衡混合物-P顺,Ç和-反式-对,Ç - (PO-OME)P
DME(2,6-二
甲基吡啶)中的Na [PO-OME]和的Pd(μ-Cl)的ME的反应生成(2,6-二
甲基吡啶)} 2在CD 2 Cl 2中在-25°C下。动力学研究揭示了二
甲基吡啶的催化和非催化的异构化途径。二
甲基吡啶催化的途径涉及经历Berry假旋转的五配位(PO-OMe)P
DMe(lut)2中间体。动力学研究,结构-活性关系,溶剂效应和非催化途径的密度泛函理论计算与最初由Nozaki,Morokuma和他的同事提出的,与κ经历五坐标过渡态的机理最一致。[PO] -
配体的3 - P,O,O配位。