ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

New data on kinetics of substituted reactions and on the interrelated effect of co.ovrddot.ordinated groups

A. A Grinberg

Technol. Ins. 'Lensoviet', Leningrad.

Abstract: The kinetic character of the trans-effect is discussed. The value of trans-activity of group A as compared with group B depends on the character of the central atom, temp., and the character of the other ligands in the inner co.ovrddot.ordinated sphere. From the data of the isotopic exchange in complex compds. it can be concluded that in K2[PdCl4] (I) and K2[PdBr4] (II) solns. the isotopic exchange of co.ovrddot.ordinated halogen ions can occur by dissocn. (hydration) and assocn.mechanisms. In the case of aq. I and II solns. exchange occurs mainly by the dissocn. mechanism. The typical complexes should be characterized not only by thermodynamic but also by kinetic parameters. There is a parallel between the speed of the isotopic exchange of the ligand and its trans-activity in the co.ovrddot.ordinated sphere of Pt(II). From the data on the speed of penetration of NH3 and pyridine mols. into PtNH3Cl3- ions a conclusion on the inner-mol. cis-effect can be made that is shown by an increased mobility and reactivity of Cl or Br atoms in cis-position to NH3 or pyridine mol. The cis-effect can manifest itself either in increasing or decreasing of the trans-effect. Exchange and substituted reactions of complex compds. by the effect of radiation of different wave lengths and in the presence of catalysts and study of the trans-effect of other elements than Pt are discussed.

Full paper in Portable Document Format: 134a201.pdf

Chemical Papers 13 (4) 201–223 (1959)