During the catalyst synthesis, both the titanium compounds and MgCl2 are packed into the silica pores. All these catalysts are activated with organoaluminum compounds such as Al(C2H5)3. All modern supported Ziegler–Natta catalysts designed for polymerization of propylene and higher 1-alkenes are prepared with TiCl4 as the active ingredient and MgCl2 as a support. Another component of all such catalysts is an organic modifier, usually an ester of an aromatic diacid or a diether. The modifiers react both with inorganic ingredients of the solid catalysts as well as with organoaluminum cocatalysts. These catalysts polymerize propylene and other 1-alkenes to highly crystalline isotactic polymers. Homogeneous catalysts A second class of Ziegler–Natta catalysts are soluble in the reaction medium. Traditionally such homogeneous catalysts were derived from metallocenes, but the structures of active catalysts have been significantly broadened to include nitrogen-based ligands. Metallocene catalysts These catalysts are metallocenes together with a cocatalyst, typically MAO, −[O−Al(CH3)]n−. The idealized metallocene catalysts have the composition Cp2MCl2 (M = Ti, Zr, Hf) such as titanocene dichloride. Typically, the organic ligands are derivatives of cyclopentadienyl. In some complexes, the two cyclopentadiene (Cp) rings are linked with bridges, like −CH2−CH2− or >SiPh2. Depending on the type of their cyclopentadienyl ligands, for example by using an ansa-bridge, metallocene catalysts can produce either isotactic or syndiotactic polymers of propylene and other 1-alkenes. Non-metallocene catalysts Ziegler–Natta catalysts of the third class, non-metallocene catalysts, use a variety of complexes of various metals, ranging from scandium to lanthanoid and actinoid metals, and a large variety of ligands containing oxygen, nitrogen, phosphorus, and sulfur. The complexes are activated using MAO, as is done for metallocene catalysts. Most Ziegler–Natta catalysts and all the alkylaluminium cocatalysts are unstable in air, and the alkylaluminium compounds are pyrophoric. The catalysts, therefore, are always prepared and handled under an inert atmosphere. Mechanism of Ziegler–Natta polymerization The structure of active centers in Ziegler–Natta catalysts is well established only for metallocene catalysts. An idealized and simplified metallocene complex Cp2ZrCl2 represents a typical precatalyst. It is unreactive toward alkenes. The dihalide reacts with MAO and is transformed into a metallocenium ion Cp2CH3, which is ion-paired to some derivative(s) of MAO. A polymer molecule grows by numerous insertion reactions of C=C bonds of 1-alkene molecules into the Zr–C bond in the ion: Many thousands of alkene insertion reactions occur at each active center resulting in the formation of long polymer chains attached to the center.