Theoretical study on electronic and steric effects of phosphorus ligands in homogeneous catalysts

A semi-empirical molecular orbital calculation, PM3 method has been employed to study the relation between the charge ρ of P atom in phosphorus ligands and the activity of homogeneous catalysts related to hydroformylation, and also to study the relation between the area S of three substituents bonding with P atom in phosphorus ligands and the selectivity of catalysts related to hydroformylation. The results indicate that, for the catalysts modified by phosphorus ligands which have similar structural characters, the P atom charge Q and the area S have a good linear relationship with the activity and selectivity of homogeneous catalysts related to hydroformylation, respectively. Here a reasonable method to predict the activity and selectivity of homogeneous catalysts modified by phosphorus ligands by means of quantum chemistry calculation is provided.