SOLVENT AND TEMPERATURE EFFECTS IN THE MECHANISM OF ALLYL AMINATION OF THE ALPHA-DIIMINE COMPLEX [PD(ETA(3)-C3H5)(C5H4N-2-CH=NC(6)H(4)OME-4)]+ BY PIPERIDINE AND MORPHOLINE

A study is reported of the solvent and temperature effects on the equi librium of alpha-diimine displacement from [Pd(eta(3)-C3H5)(N-N')](+) (N-N' = C5H4N-2-CH=NC(6)H(4)OMe-4) by piperidine and morpholine and on the rates of allyl amination by these amines in the presence of activ ated olefins (ol) leading to [Pd(eta(2)-ol)(N-N')] in either chlorofor m or methanol, The larger extent of alpha-diimine displacement in chlo roform is essentially governed by entropy factors. Delta H degrees and Delta S degrees values for the equilibrium are discussed. The activat ion parameters for the slow amination reaction indicate that the react ivity differences observed are determined mainly by the entropic facto r, as far as the solvent effect is concerned.