Investigation of ion pair formation in the triphenylmethyl chloride–trimethyl aluminium system, as a model for the activation of olefin polymerization catalyst

Abstract

Triphenylmethyl chloride (“trityl chloride”, Ph 3CCl) will transfer chloride ions to aluminium alkyls and methylaluminoxane and it is thereby converted into 1,1,1-triphenylethane (“trityl methyl” Ph 3CMe) and the triphenylcarbonium ion (“trityl ion”, Ph 3C +). IR spectra of these trityl species have been recorded. Assignments are supported by quantum chemical calculations, leading to significant revisions for some of the modes that are most influenced by reactions. A bright yellow colour shown to be due to the trityl cation, makes trityl chloride a useful indicator for ion pair formation. Trimethyl aluminium (TMA) is chlorinated by trityl chloride and forms dimethyl aluminium chloride (DMAC). DMAC will form a stable ion pair with trityl chloride, probably by forming the anion Al 2Cl 3Me 4 −. Large excess of trityl chloride causes the formation of AlCl 4 −, and probably AlCl 3Me − and AlCl 2Me 2 − anions. It appears that methyl aluminium chloride anions are formed if, and only if, the anions have at least three chlorine atoms, possibly because of the need to dissipate the negative charge enough to keep the anion dissolved in the hydrocarbon solvent. Methylaluminoxane (MAO) also forms ion pair with trityl chloride, although to lesser extent and less persistent.