Department of Chemistry, University of Cape Town, Private Bag, Rondebosch, 7700, South Africa.
Dalton Trans. 2013 Aug 21;42(31):11163-79. doi: 10.1039/c3dt51283e.
The reaction of cis-[PtCl₂(dmso)] with the salicylaldimine ligand, N-(2-hydroxybenzylidene)-2,6-di-isopropylaniline, LA in the presence of sodium acetate in methanol produced both cis- and trans-[PtClLA(dmso)], 1a and 1b. An analogous reaction for the less bulky ligand, N-(2-hydroxybenzylidene)aniline LB produced only cis-[PtClLB(dmso)], 2. The reactions of these dmso complexes with triphenylphosphine also yielded complexes with different geometries depending on the nature of the salicylaldiminato ligand. Thus the cis-trans isomerization of cis-[PtClLA(PPh₃)] 3a was investigated both experimentally and computationally, and a tetrahedral transition state was detected in this process. A good agreement of the experimental activation parameters with those determined theoretically using DFT was obtained. LA was also reacted with [PtClMe(cod)] in methanol to yield the corresponding salicylaldiminato complex 6 in which the methyl group is cis to the imine nitrogen. X-ray crystal structures of some compounds obtained are reported.
顺式-[PtCl₂(dmso)]与水杨醛亚胺配体 N-(2-羟基苯亚甲基)-2,6-二异丙基苯胺（LA）在甲醇中，在醋酸钠存在的条件下反应，生成顺式和反式-[PtClLA(dmso)]，1a 和 1b。对于体积较小的配体 N-(2-羟基苯亚甲基)苯胺（LB），类似的反应只生成顺式-[PtClLB(dmso)]，2。这些 dmso 配合物与三苯基膦的反应也产生了不同几何形状的配合物，这取决于水杨醛亚胺配体的性质。因此，实验和计算研究了 cis-[PtClLA(PPh₃)]3a 的顺反异构化，在此过程中检测到了一个四面体形过渡态。实验活化参数与使用 DFT 理论确定的参数非常吻合。LA 还与[PtClMe(cod)]在甲醇中反应，生成了相应的水杨醛亚胺配合物 6，其中甲基处于亚胺氮的顺式位置。报道了一些获得的化合物的 X 射线晶体结构。
