Ketoximate Derivatives of Titanium Alkoxides and Partial Hydrolysis Products Thereof

Crystalline oximate derivatives of titanium alkoxides [Ti(OR)(2)-(ON = CR'R '')(2)](2) were obtained when Ti(OR)(4) (R = iPr, 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(OiPr)(3)(ON = C6H10)](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. Ti6O6(OiPr)(6)(ON = CR2)(6) (CR2 = CMe2 or C5H8) and Ti4O2(OiPr)(8)(ON = CMe-CH2-CMe = NO)(2) were also structurally characterized. In these derivatives the NO groups bridge two titanium atoms. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)