Di-tert-butylcatecholate derivatives of titanocene

Abstract

Reaction of Cp₂TiCl₂ (Cp = η⁵-C₅H₅) with sodium 3,6-di-tert-butylcatecholate (Na₂Cat³⁶) leads to mononuclear complex [Cp₂TiCat³⁶], while the isomeric sodium 3,5-di-tert-butylcatecholate (Na₂Cat³⁵) gives the mixed-valence binuclear complex [Cp₂Ti(μ-Cat³⁵)₂TiCp]. The latter was characterized by EPR spectroscopy and magnetic susceptibility measurements, and shown to be a Ti-centred radical. DFT calculations confirm that the unpaired electron is located on the Ti atom from the TiCp₂ fragment.