摘要: As one of the most important catalysts in polyethylene industry, Phillips catalyst (CrOx/SiO2) was quite unique for its activation by ethylene monomer without using any activator like alkyl-aluminium or MAO. In this work, the density functional theory (DFT) calculation combined with paired interacting orbitals (PIO) method was applied for the theoretical studies on coordination reaction mechanism between ethylene monomer and two model catalysts namely Cr(II)(OH)2 (M1) and silsesquioxane-supported Cr(II) (M2) as surface Cr(II) active site precursors on Phillips catalyst at the early stage of ethylene polymerization. Unexpected multiplicity of the coordination states of ethylene monomer on both M1 and M2 model catalysts had been first reported on a molecular level. In general, increasing the coordination numbers of ethylene, the corresponding binding energy per ethylene for all the complexes was decreased. The supporting effect of chromium oxide onto silica gel surface was found to be destabilizing the corresponding complexes and decreasing the multiplicity of the coordination states as well due to both electronic and steric effect. Moreover, tri- and tetra- or higher ethylene coordination states could not be possibly formed on the supported catalyst as on the Cr(II)(OH)2. The optimized complex geometries were adopted for determining the intermolecular orbital interactions. In-phase overlap orbital interaction for all the molecular complexes indicated favorable coordination between ethylene and Cr(II) sites. The molecular orbital origin of the π-bonded Cr(II), and mono- and di-C2H4 M1 complexes had been elucidated by PIO method showing high possibility of the formation of metallacyclopropane or metallacyclopentane active sites in the subsequent initiation of polymerization stage.