CIS-EFFECT OF DIMETHYL SULFIDE AND LEAVING GROUP EFFECT IN REACTIONS OF THE CATIONIC COMPLEX CHLORO (DIMETHYL SULFIDE) (1,2-DIAMINOETHANE)PLATINUM(II) CHLORIDE
CIS-EFFECT OF DIMETHYL SULFIDE AND LEAVING GROUP EFFECT IN REACTIONS OF THE CATIONIC COMPLEX CHLORO (DIMETHYL SULFIDE) (1,2-DIAMINOETHANE)PLATINUM(II) CHLORIDE
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DOI：
10.1021/ic50225a030
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发表时间：
1981-01-01
影响因子：
4.6
通讯作者：
TOBE, ML
中科院分区：
文献类型：
--
作者：
BONIVENTO, M;CANOVESE, L;TOBE, ML
[Pt (dms)(en) X] I+（dms=二甲基硫化物，en= 1,2 -二氨基乙烷）取代X的动力学在25.0℃的水中，研究了各种亲核试剂（Br “， I”， N3“， SCN”， S032", NH3, SC （NH2) 2, H20）对X= Cl或I （zi= 1）或H20 (zi= 2)）的反应，发现1+阳离子底物的logk2 （k2是μ = 0时的二阶速率常数）与标准1+阳离子底物[Pt (NH3)(en) Cl]+的亲核性指数rCp之间存在良好的线性关系。本文将所得数据与文献资料相结合，讨论dms与Me2SO （Me2SO二甲亚砜）和NH3的动力学顺式效应，并讨论其离去基效应。将水络合物[Pt (dms)(en) H20] 2+与其他双阳离子水系的相对排水量数据进行了比较。
The kinetics of the replacement ofX from [Pt (dms)(en) X]'I+(dms= dimethyl sulfide; en= 1, 2-diaminoethane; X= Cl or I (zi= 1) or H20,(zi= 2)) by a variety of nucleophiles (Br “, I", N3", SCN", S032", NH3, SC (NH2) 2, H20) have been studied in water at 25.0 C. Good linear relationships havebeen observed between log k2 for the 1+ cationic substrates (k2 is the second-order rate constant at µ= 0) and the index of nucleophilicity, rCp,, relative to the standard 1+ cationic substrate [Pt (NH3)(en) Cl]+. The data obtained have been used, together with data taken from the literature, in order to discuss the kinetic cis effect of dms as compared to thatof Me2SO (Me2SO dimethyl sulfoxide) and NH3 and also to discuss the leavinggroup effect. The data relative to the displacement of water from the aquo complex [Pt (dms)(en) H20] 2+ have been compared with those relative to other bis-cationic aquo species.