Titanium oxo carboxylate compounds. Crystal and molecular structures of [{TiCl2(O2CEt)(ETCo2H)}2O] and [Ti3Cl3O2(O2CEt)5] and an unusual quantitative conversion of a Ti2O to a Ti3O2 oxo derivative
- 1 January 1994
- journal article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 24,p. 3533-3538
- https://doi.org/10.1039/dt9940003533
Abstract
Reaction of TiCl4 with alkyl carboxylic acids RCO2H (R = Me, Et or But) using a 1:1 (Ti:acid) molar ratio at 0°C yielded the dinuclear chloro carboxylates [Ti2Cl7(O2CR)(RCO2H)](R = Et or But). When a 1:2.5 ratio is used at 25°C oxygen abstraction occurs to yield [(TiCl2(O2CR)(RCO2H)}2O](R = Me, Et or But). When R = Et another product, [Ti2Cl3O(O2CEt)3(EtCO2H)], was also obtained. At 40–70°C the oxo compounds (R = Et or But) decompose quantitatively to form the trinuclear species [Ti3Cl3O2(O2CR)5], but the compound with R = Me remains unchanged up to 110°C. The co-ordinated acid in [(TiCl2-(O2CR)(RCO2H)}2O] is displaced by tetrahydrofuran (thf) to yield [{TiCl2(O2CR)(thf)}2O](R = Me, Et or But), and in contrast to the former, these species are stable up to 110°C. The crystal structures of [{TiCl2(O2CEt)(EtCO2H)}2O] and [Ti3Cl3O2(O2CEt)5] have been determined, and show [Ti(µ-O)-(µ-O2CR)2Ti] and [Ti3(µ-O)(µ3-O)] cores respectively. The comparative reactivity of alkyl and aryl acids towards TiCl4 is discussed.Keywords
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