X-ray crystal structures on the hydrolysis path of [{Ti(C 5Me 4R)F 3} 2]: Water adduct [{Ti(C 5Me 4Et)F 3} 2(H 2O)]·(H 2O), oxoaqua complex [Ti 7F 21O(C 5Me 4Et) 5(H 2O) 2] and oxo complex [Ti 8F 22O 2(C 5Me 4H) 6]·2CHCl 3

Abstract

Sublimation of [{Ti(C 5Me 4Et)F 3} 2] in the presence of hydrated molecular sieves afforded crystals of dititanate [{Ti(C 5Me 4Et)F 3} 2(H 2O)]·(H 2O) ( 1·H 2O) with three bridging fluorines, terminally coordinated aqua ligand, and hydrogen-bonded non-coordinated water molecule. The crystallization of [{Ti(C 5Me 4R)F 3} 2] (R = Et, H) from solutions with H 2O:Ti ratio below one afforded mixed fluoro-oxo organotitanate clusters [Ti 7F 21O(C 5Me 4Et) 5(H 2O) 2] ( 2) and [Ti 8F 22O 2(C 5Me 4H) 6]·2CHCl 3 ( 3·2CHCl 3), respectively. The clusters could be considered as intermediates in the hydrolysis process of [{Ti(C 5Me 4R)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(C 5H 5)F 3} 2(H 2O)]·(H 2O) closely resembles the 1·H 2O compound.