The role of free ions in reactions of olefins with soluble complex catalysts

It was found that in the homogeneous catalytic system (C 5 H 5 ) 2 TiCl 2 + Al(CH 3 ) 2 Cl the catalytic activity is due to the presence of free ions, presumably (C 5 H 5 ) TiCH 3 formed in the equilibrium: (C 5 H 5 ) 2 TiCH 3 Cl. AlCH 3 Cl 2 ⇄ (C 5 H 5 ) 2 Ti + CH 3 + Al(CH 3 ) Cl 3 ‐ Further evidence for the suggested mechanism has been found. By means of electrodialysis the formation of positive ions containing Ti was shown. Catalytic activity appears only in the presense of the latter. The increased cataivtiy activity in comparatively polar solvents (CH 2 Cl 2 , C 2 H 4 Cl 2 ) is connected with the increased number of the ions. The linear dependence of log k ( k is the rate constant of the reaction of free ion with an olefin) with 1/D (D is the dielectric constant) was found in five different solvents and their mixtures.