Structural characterization of Ti centres in Ti-silicalite and reaction mechanisms in cyclohexanone ammoximation

The main results obtained by means of many physical methods (IR, Raman, UV-Vis and XAFS spectroscopies) concerning the structure of the Ti centre in titanium silicalite and the reaction intermediates in the ammoximation of cyclohexanone are concisely reviewed.

The Ti is in tetrahedral coordination in vacuo and expands its coordination sphere upon interaction with adsorbates. In the presence of H₂O and H₂O/H₂O₂ solutions one of the SiOTi bridges is hydrolyzed with formation of (SiO)₃L₂TiOH (LH₂O) and (SiO)₃L₂TiOOH species, respectively. When NH₃ is dosed on (SiO)₃L₂TiOOH structures (SiO)₃L₂TiOO^?NH₄⁺ species are formed. These species are thought to play an important role in the ammoximation reaction. The geometries of the peroxidic species (open or bridged) are discussed also on the basis of ab initio calculations.