Controlled assembly of a heterogeneous single-site ethylene trimerization catalyst as probed by X-ray absorption spectroscopy.
X-ray absorption spectroscopy at the Cr K- and L(2,3)-edges was used to study the assembling process of a heterogeneous Cr-based single-site catalyst. The starting point was a Phillips-type system with monochromate species anchored on a silica surface, which was first reduced to a variety of different surface Cr(II) species. The reduced sample was modified with a 1,3,5-tribenzylhexahydro 1,3,5-triazine (TAC) ligand in the presence of CH(2)Cl(2) as solvent to yield a heterogeneous single-site Cr-based catalyst active in the trimerization of ethylene. The molecular structure of the resultant catalytic material consists of distorted octahedral Cr(III) species. The extended X-ray absorption fine-structure (EXAFS) spectroscopy fitting procedure in R space up to 2.5 A showed that the synthesis leads to coordination with a TAC ligand. The fit also shows that it was possible to complete the six-fold environment around Cr(III) with two oxygen atoms and one chloride ligand. This chloride ligand is formed in a redox process from the solvent and is responsible for the oxidation of surface Cr(II) to Cr(III). The obtained geometry and the local environment of the surface complex are discussed in light of its homogeneous counterpart and confirm the single-site characteristics of the prepared catalytic material.
Nenu
Cristina N
CN
Inorganic Chemistry and Catalysis, Department of Chemistry, Utrecht University, PO Box 80083, 3508 TB Utrecht, The Netherlands.
van Lingen
Joost N J
JN
de Groot
Frank M F
FM
Koningsberger
Diek C
DC
Weckhuysen
Bert M
BM