Titanocene dichloride Cp₂TiCl₂ was found to be a novel and efficient catalyst for the transesterification between dimethyl carbonate and phenol to produce diphenyl carbonate. Cp₂TiCl₂ is more stable in air and more convenient for industrial application than titanium esters. Various titanocene complexes were used as catalysts for the transesterification on the basis of Cp₂TiCl₂. It was found that titanocene catalysts modified by various substituents would strongly influence the steric and electronic properties of the catalytic centers, the stability of the transition states, and their catalytic behaviors. When the substituent was smaller and more electron withdrawing, or the substituent could make the transition state more stable, the reaction would take place with better results.

Key words: dimethyl carbonate, diphenyl carbonate, titanocene dichloride, titanocene complex, transesterification