摘要
高效液相色谱法(HPLC)研究液相反应动力学是从二(N,N-二烷基二硫代氨基甲酸)螯合物间的配体交换反应动力学开始的。HPLC由于其分辨率高和检测浓度低,在研究反应物和产物的结构和物理化学性质极为相似的反应中显示出独特的本领。本文在12—32℃研究了二(烷基黄原酸)合钯(Ⅱ)间的配体交换反应动力学。
The kinetics of ligand exchanges between bis (alkylxanthato) palladium (Ⅱ) have
been studied at the temperature range 12--32℃. The equilibrium constants K
determined are always 4.0±0.5, consistent with the value calculated statistically. It
is found that both the forward and backward reactions are in second-order. The
isokinetic relationships have been observed with isokinetic temperature β=293±6K in
the first reaction series when R=Et, n-Pr, n-Bu, i-Bu and with β=285±25K in the
second reaction series when R=Me, n-Bu, i-Bu, Am (Chinese text, eqn. 7 and 8
respectively). The decreasing series of the first reaction for R-n-Pr in various
solvents has been found as CCl_4>CHCl_3>CH_2Cl_2. An eight-membered ring species is
supposed to be formed as the intermediate in the rate-determining step.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
1989年第3期288-292,共5页
Acta Chimica Sinica
基金
国家自然科学基金
