X-ray crystal structures on the hydrolysis path of [{Ti(C5Me4R)F3}2]: Water adduct [{Ti(C5Me4Et)F3}2(H2O)]·(H2O), oxoaqua complex [Ti7F21O(C5Me4Et)5(H2O)2] and oxo complex [Ti8F22O2(C5Me4H)6]·2CHCl3

Sublimation of [{Ti(C5Me4Et)F3}2] in the presence of hydrated molecular sieves afforded crystals of dititanate [{Ti(C5Me4Et)F3}2(H2O)]·(H2O) (1·H2O) with three bridging fluorines, terminally coordinated aqua ligand, and hydrogen-bonded non-coordinated water molecule. The crystallization of [{Ti(C5Me4R)F3}2] (R = Et, H) from solutions with H2O:Ti ratio below one afforded mixed fluoro-oxo organotitanate clusters [Ti7F21O(C5Me4Et)5(H2O)2] (2) and [Ti8F22O2(C5Me4H)6]·2CHCl3 (3·2CHCl3), respectively. The clusters could be considered as intermediates in the hydrolysis process of [{Ti(C5Me4R)F3}2]. The quantum–mechanical calculation reveal that monodentate-bonded ligand in complex 1 is energetically favoured over the more intriguing bidentate bridging one. The calculated geometry of model compound [{Ti(C5H5)F3}2(H2O)]·(H2O) closely resembles the 1·H2O compound.