Intramolecular alkoxide-tethered permethyltitanocene(III) complexes – synthesis and crystal structure

Abstract

Singly tucked-in titanocene [Ti(III)(η5-C5Me5)(η5:η1-C5Me4CH2)] (1) reacted readily with di-tert-butyl ketone and 2,4,6-trimethylacetophenone to give permethyltitanocene derivatives [Ti(III)(η5-C5Me5){η5-C5Me4CH2C(t-Bu)2O-κO}] (2) and [(Ti(III)(η5-C5Me5)-{η5-C5Me4CH2CMe(C6H2Me3)O-κO}] (3) with the tetramethylcyclopentadienyl ring tethered to the titanium atom by ethoxy group disubstituted at Cα. Crystal structures of 2 and 3 showed that the Ti–O bond is only slightly inclined to the tethered cyclopentadienyl ligand, and the bulky mesityl or tert-butyl substituents did not impose an observable steric hindrance into molecules of 2 and 3. Whereas the Ti–O bond lengths in 2 and 3 do not significantly differ, a higher wavenumber of the 1a1 → b2 electronic transition for 2 (7326 cm–1) compared with that for 3 (6666 cm–1) indicates a more efficient oxygen-to-titanium π-electron back donation in 2. This is induced by two electron-donating tert-butyl groups on Cα compared with a combined effect of electron-donating methyl and electron-attracting mesityl substituents in 3.