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
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摘要: Abstract The kinetics of anation Pd(1,1,7,7-Et 4 dien)OH 2+ 2 and Pd(1,1,4-Et 3 by chloride ion were studied under pressures up to 1 kbar using a high pressure stopped-flow system. construction testing the latter system are discussed in detail. rate activation parameters for above reactions are: k(25 °C) = 4.2 ± 0.1 1558 68 M −1 sec ; ΔH≠ 13.4 0.4 10.5 0.7 kcal mol ΔS≠ −10.7 1.2 −8.7 2.3 cal K ΔV≠ −3.0 0.2 −2.7 cm , respectively. These considered as evidence an associative type process.
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