摘要
研究了二(境基黄原致)合铂(Ⅱ)[Pt(S_2COR)_2(R=Me,Et,n-Pr,n-Bu,Am)]与哌啶连串取代反应动力学,提出了包括前期平衡的反应机理,据此导出的速率方程圈满地解释了全部实验事实.计算了前期平衡常数和速控步骤的速率常数,并对加成物的结构作了合理推断,计算了各活化参数和两个反应系的等动力学温度β_1=283±7K和β_2=263±25K.
The title reactions have been studied by spectrophotometry.The products of the first and second steps of the substitution reactions are Pt(S2COR)(S2CN(CH2)5)and Pt(S2CN(CH2)5)2 respectively.The reaction order in each of the complexes is unity,and the apparent reaction orders in piperi-dine are in the ranges of 2.0 to 2.6 and 1.5 to 1.9 respectively.A mechanism involving an additive preequilibration was proposed.The rate equation derived from the mechanism explained all of the experimental results satisfactorily.The preequilibrium constants and the rate constants of the rate determining steps were calculated,and the structures of the adducts were discussed and reasonably infered,Activation parameters and isokinetic temperatures(β1=283±7K,β2=263±25K)were calculated.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
1992年第12期1572-1576,共5页
Chemical Journal of Chinese Universities
基金
国家自然科学基金
关键词
烷基黄原酸
铂
哌啶
连串取代反应
Bis(alkylxanthato)platinium(II),Piperidine,Consecutive substitution reaction,Kinetics and mechanism
