Reactions of titanocene dihalides with N,N ',N ''-chelates: Preparation, X-ray structure and characterization of bis(chloro){2,6-bis[(3,5-dimethyl)pyrazol-1-yl]pyridine}(eta(2)-peroxo)t itanium(IV)

摘要

The reaction of [Ti-IV(Cp)(2)Cl-2] (Cp- = eta(5)-C5H5-) and 2,6-bis(3,5-dimethylpyrazolyl-1-yl)pyridine (bdmpp) in Me2CO has afforded complex [(TiCl2)-Cl-IV(O-2)(bdmpp)] (1). The complex can also be prepared from the 1:1:1 [Ti(Cp)(2)Cl-2]/bdmpp/H2O2 reaction mixture in various solvents. Single-crystal, X-ray crystallography has revealed that the Ti-IV center is in a distorted pentagonal bipyramidal environment in both of the two, crystallographically independent molecules that are present in the asymmetric unit; the equatorial positions are occupied by the two O atoms of the side-on (eta(2)) O-2(2-) group and the three N-atoms of the tridentate chelate, while the two chloro ligands are on the axial positions. IR, Raman, electronic and H-1 NMR data are discussed in terms of the known structure and the coordination modes of the peroxo and bdmpp ligands.