Kinetics of anation in platinum(II) and palladium(II) complexes of N-alkylated diethylenetriamine
作者:Luciano Canovese、Matteo Cusumano、Antonino Giannetto
DOI:10.1039/dt9830000195
日期:——
concentration. The kinetic behaviour of the complexes depends markedly on the size of the substituents at the nitrogen atoms in the ligand L–L–L. When L–L–L = Me2N[CH2]2NMe[CH2]2NMe2 the second-order rate constants follow the usual nucleophilicity scale and in the case of the platinum complex the kinetic behaviour can be related to that of the unhindered complex [Pt(dien)(H2O)]2+(dien = H2N[CH2]2NH[CH2]2NH2)
置换H的动力学2 Ó在伪八面体配合物[铂(L-L-L)(H 2 O)] [CLO 4 ] 2(L-L-L =我2 N [CH 2 ] 2 NME [CH 2 ] 2 NMe 2)和[Pd(L–L–L)(H 2 O)] [ClO 4 ] 2(L–L–L = R 2 N [CH 2 ] 2 NMe [CH 2 ] 2 NR 2,R = Me或Et]由亲核试剂Cl –,Br –,I –,(NH 2)在25°C的水中对2 CS,SCN –和S 2 O 3 2 –进行了研究。所有反应都显示出对底物和亲核试剂浓度的一阶依赖性。配合物的动力学行为明显取决于配体L–L中氮原子上取代基的大小。当L–L–L = Me 2 N [CH 2 ] 2 NMe [CH 2 ] 2 NMe 2时,二级速率常数遵循通常的亲核尺度,在铂络合物的情况下,动力学行为可能与不受阻碍的络合物[Pt(dien)(H 2 O)] 2+(dien