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)F-3)(2)] in the presence of hydrated molecular sieves afforded crystals of dititanate [[Ti(C5Me4Et)F-3}(2) (H2O)](.)(H2O) (1(.)H(2)O) with three bridging fluorines, terminally coordinated aqua ligand, and hydrogen-bonded non-coordinated water molecule. The crystallization of [(Ti(C5Me4R)F-3}(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)](.)2CHCl(3) (3(.)2CHCl(3)), respectively. The clusters could be considered as intermediates in the hydrolysis process of [{Ti(C5Me4R)F-3)(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)F-3}(2)(H2O)(.)(H2O) closely resembles the 1(.)H(2)O compound. (c) 2005 Elsevier B.V. All rights reserved.