Abstract
The constrained geometry alkoxide [Ti(III)(eta(5)-C5Me5){eta(5)-C5Me4CH2CMe2O-kappa O}] (2) and titanocene alcoholates [Cp*2TiOR] for R = 1-adamantyl (3) and pentafluorophenyl (4) were prepared by reacting acetone and the respective alcohols with the singly tucked-in titanocene [Ti(III)(eta(5)-C5Me5)(eta(5):eta(1)-C5Me4CH2)] (1) in order to add the simplest member to constrained geometry alkoxides 5 and 6 and to extend the series of [Cp*2TiOR] (R = Me (8), 'Bu (7), Ph (9), and H (10)) compounds for one of the most bulky and the most electron attracting substituent. The titanocene alkoxides with the alkoxy carbon atom tethered to one of the cyclopentadienyl ligands showing the crystallographic Ti-O-C angle close to 133 degrees are a suitable group of compounds to be compared with the [Cp*2TiOR] compounds, where the Ti-O-C angle is about 174 degrees for 3 and 7 and 180 degrees for 4.