Role of the Metal Oxidation State in the SNS−Cr Catalyst for Ethylene Trimerization:  Isolation of Di- and Trivalent Cationic Intermediates

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ABSTRACTA range of transition metal bearing hollandite phases, formulated Ba1.2B1.2Ti6.8O16 (B2+ = Mg, Co, Ni, Zn, Mn) and Ba1.2B2.4Ti5.6O16 (B3+ = Al, Cr, Fe) were prepared using an alkoxide - nitrate route. X-ray powder diffraction demonstrated the synthesis of single phase materials for all compositions except B = Mn. The processing conditions required to produce > 95 % dense ceramics were determined for all compositions, except B = Mg for which the maximum density obtained was > 93 %. Analysis of transition metal K-edge XANES data confirmed the presence of the targeted transition metal oxidation state for all compositions except B = Mn, where the overall oxidation state was found to be Mn3+. The K-edge EXAFS data of Ba1.2B1.2Ti6.8O16 (B = Ni and Co) were successfully analysed using a crystallographic model of the hollandite structure, with six oxygen atoms present in the first co-ordination shell at a distance of ca. 2.02Å. Analysis of Fe K-edge EXAFS data of Ba1.2B2.4Ti5.4O16 revealed a reduced co-ordination shell of five oxygens at ca. 1.99Å.


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