Volumes of activation for the anation of Pd(II) substituted dien complexes by chloride ion in aqueous solution. A high pressure stopped-flow instrument for studying the kinetics of fast reactions under pressure
作者:R. Van Eldik、D.A. Palmer、R. Schmidt、H. Kelm
DOI:10.1016/s0020-1693(00)83732-9
日期:1981.1
Abstract The kinetics of anation of Pd(1,1,7,7-Et 4 dien)OH 2+ 2 and Pd(1,1,4-Et 3 dien)OH 2+ 2 by chloride ion were studied under pressures up to 1 kbar using a high pressure stopped-flow system. The construction and testing of the latter system are discussed in detail. The rate and activation parameters for the above reactions are: k(25 °C) = 4.2 ± 0.1 and 1558 ± 68 M −1 sec −1 ; ΔH≠ = 13.4 ± 0.4
摘要研究了Pd(1,1,7,7-Et 4 dien)OH 2+ 2和Pd(1,1,4-Et 3 dien)OH 2+ 2在最高压力下的阴离子化动力学。使用高压停止流系统时为1 kbar。详细讨论了后者系统的构建和测试。上述反应的速率和活化参数为:k(25℃)= 4.2±0.1和1558±68M -1 sec -1;ΔH≠= 13.4±0.4和10.5±0.7 kcal mol -1; ΔS≠= -10.7±1.2和-8.7±2.3 cal K -1 mol -1; 和ΔV≠= -3.0±0.2和-2.7±0.2cm 3 mol -1。这些被认为是关联类型的动画过程的证据。