Kuhn, AnnemarieTischlik, SonjaHopmann, Kathrin H.Landman, MarileVan Rooyen, Petrus H.Conradie, Jeanet2016-10-122016-11Kuhn, A, Tischlik, S, Hopmann, KH, Landman, M, Van Rooyen, PH & Conradie, J 2016, 'Structure, substitution and hydrolysis of Bis(trifluorobenzoylacetonato-O,O′)dichloro titanium(IV) : an experimental and computational study', Inorganica Chimica Acta, vol. 453, pp. 345-356.0020-169310.1016/j.ica.2016.08.034http://hdl.handle.net/2263/57109The chlorine coordinated ligands in [Ti(tfba)2Cl2] (Htfba = 4,4,4-trifluoro-1-(phenyl)-1,3-butanedione = PhCOCH2COCF3) are very susceptible to hydrolysis and even with trace amounts of water, the formation of hydrolysed complexes, dinuclear {Ti(tfba)2Cl}2(μ-O) or tetranuclear [Ti(tfba)2(μ-O)]4, take place, whereas with an excess of water, decomposition to TiO2 occurs. Substitution of the chloro-ligands in [Ti(tfba)2Cl2] with H2biphen (H2biphen = 2,2′-dihydroxybiphenyl or biphenol) leads to [Ti(tfba)2biphen] with enhanced water stability. Experimentally, two steps were observed for the substitution [Ti(tfba)2Cl2] + H2biphen. Computational chemistry calculations reveal that each step involves several transition states, with formation of a 7-coordinated intermediate in the first reaction half. Location of this intermediate is dependent on inclusion of empirical dispersion-corrections in the functional. The three geometrical cis-isomers of [Ti(tfba)2biphen] were observed in solution using low temperature 1H and 19F NMR, whereas in the solid state, two of the isomers, cis-cis-trans and cis-trans-cis, crystallized in the same unit cell. The crystal structure of the hydrolysed tetranuclear complex [Ti(tfba)2(μ-O)]4 is composed of four identical cis-cis-trans isomers of [Ti(tfba)2Cl2]. The eight β-diketonato backbones and the four bridging oxygens have a S4 molecular symmetry.en© 2016 Elsevier B.V. All rights reserved. Notice : this is the author’s version of a work that was accepted for publication in Inorganica Chimica Acta. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. A definitive version was subsequently published in Inorganica Chimica Acta, vol. 453, pp. 345-356, 2016. doi : 10.1016/j.ica.2016.08.034.TitaniumSubstitutionHydrolysisBeta-diketonePostprint Article