Facile generation of bimetallic titanium alkoxides with silacycloalkyl- or silacycloalkenyldiamide ligands: Oxo-insertion involving dimerization or rearrangement

Abstract

The reaction between the spirosiladiazatitanacyclobutane complexes (cyclo)Si(NBut)(2)TiMe2 (1) and (cyclo)Si(NBut)(2)TiMeCl (3a) and dioxygen proceeds by insertion of an oxygen molecule into a Ti-C bond of 1 and 3a, yielding methoxy-bridged titanium dimer [(cyclo)Si(NBut)(2)Ti(mu -OMe)Me](2) (2) or [(cyclo)Si(NBut)2Ti(mu -OMe)Cl](2) 4a), respectively. In contrast, the reaction of the titanium(IV) dichloride complex (cyclo)Si(NBut)(2)-TiCl2 (5a) with O-2 gives hydrazido complete [{((NBuNBut)-N-t-(cyclo)SiO}TiCl2](2) (6a) as a result of facile formation of the Si-O-Ti bonds upon autoxidation.