New crystalline complex chlorides containing transition metal chlorides or oxychlorides as components of coordination catalysts

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Abstract
Novel complex chlorides have been obtained by reacting TiCl4, VOCl3, MoOCl4, WOCl4, or AlCl3, with Be, Mg, Ca, or Sr chlorides in the presence of electron donors such as POCl3(L) or C6H5POCl2, (L′). The resulting products, obtained with good yield, show defined stoichimetry, ionic character, and crystalline structure, and may be considered reference systems for high‐yield catalysts in the low‐pressure polymerization of ethylene (HDPE). Complexes (TiCl6)MgL6, (TiCl5L′)2MgL′6, and (Ti2Cl10)MgL6associated with (i‐C4H9)3Al were found very active in HDPE synthesis, but completely unable to polymerize propylene. This result and other evidence suggest that part of the catalytic activity of these systems is displayed by soluble species. The role played by the Mg ion in high‐yield catalysts is displayed by soluble species. The role played by the Mg ion in high‐yield catalysts is discussed in the light of the peculiar behavior shown by the complex chlorides containing this earth‐alkali metal.