作者:Lucio Cattalini、Francesca Guidi、Martin L. Tobe
DOI:10.1039/dt9930000233
日期:——
The cis- and trans-[Pt(am)2Cl2] isomers (am = dimethylamine, pyridine, 4-cyanopyridine, 4-chloropyridine, 2-methylpyridine, 4-methylpyridine, 2,4-dimethylpyridine, 4-ethylpyridine, morpholine or piperidine), react rapidly with excess CN- in methanol to form the corresponding cis- and trans-[Pt(am)2(CN)2] species which then react further to give [Pt(CN)4]2-. The kinetics of the slow step, [Pt(am)2(CN)2] + CN- --> [Pt(am)(CN)3]- + am, has been studied. In spite of the strong trans effect of CN- the trans species are all more reactive than the corresponding cis isomers. The second-order rate constants are sensitive to the nature of am; plots of log k2 against the pK(a) of Ham+ are linear but the slope for the trans isomers (-0.27) is much greater than that for the cis isomers (-0.07). The rate constants for the displacement of o-methyl substituted pyridines are smaller than predicted from their basicity. This steric hindrance effect is much more marked in the trans isomers. The complexes with am = NH3 and NH2Me are similarly less reactive than might be predicted but the effect is the same in both isomers. The results are explained in terms of the trans effect of cyanide and its effect upon the intrinsic reactivities and nucleophilic discriminations of the substrates.