Ketoximate Derivatives of Titanium Alkoxides and Partial Hydrolysis Products Thereof

Abstract

Abstract Crystalline oximate derivatives of titanium alkoxides [Ti(OR) 2 (ON=CR′R″) 2 ] 2 were obtained when Ti(OR) 4 (R = i Pr, Et) was treated with various oximes (cyclopentanone oxime, cyclohexanone oxime, acetoxime, ethyl methyl ketoxime or 2,4‐pentandione dioxime). Formation of bis‐substituted derivatives was favored in each case, and only one mono‐substituted derivative, [Ti(O i Pr) 3 (ON=C 6 H 10 )] 2 , was isolated. Two isomers were observed for [Ti(OR) 2 (ON=CR′R″) 2 ] 2 , differing by the mutual orientation of the oximate ligands. The NO groups of the oximate ligands are side‐on coordinated to one titanium atom in each case. Three partially hydrolyzed derivatives, viz. Ti 6 O 6 (O i Pr) 6 (ON=CR 2 ) 6 (CR 2 = CMe 2 or C 5 H 8 ) and Ti 4 O 2 (O i Pr) 8 (ON=CMe–CH 2 –CMe=NO) 2 were also structurally characterized. In these derivatives the NO groups bridge two titanium atoms.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)