Synthesis, characterization and catalytic activity of the complex titanium bis(dimethylmalonate)–bis(diethylamido) in the polymerization of propylene

In this account we present the synthesis, characterization and catalytic activity in the polymerization of propylene of a bis(dimethyl malonate) titanium bis(diethylamine) complex (1). The complex exhibits in solution a dynamical isomerization following an internal Bailar twist. The activation of complex 1 was obtained by its reaction with methylalumoxane (MAO). The activated complex in solution shows a different dynamic process involving an equilibrium between a monodentate η1 and bidentate η2 binding of the dimethylmalonate ligand to the metal center. This equilibrium is responsible for the formation of, at least, two active species for the polymerization reaction bearing major symmetry differences. The monodentate coordination (opened form) of the ligand was found to be the major form of the active species of the complex when activated with MAO, most probably due to a strong interaction of the oxygen atoms in the ligand with the strong Lewis acid co-catalyst. The active species in the polymerization were studied by NMR and ESR spectroscopies. The resulting polypropylene showed elastomeric properties with low tacticites.

Graphical abstractThe synthesis, characterization and catalytic activity of bis(dimethylmalononate)titanium bis(diethylamine) complex (1) is presented. Complex 1 undergoes a Bailar isomerization in solution. With methylalumoxane (MAO), the complex yields a cationic closed (4) and opened (5) forms of the cationic complex, each of which is responsible for the formation of a different polypropylene.Figure optionsDownload full-size imageDownload as PowerPoint slide