A mixed-valence (Ti III Ti IV ) carboxylate complex: crystal structures and properties of [Ti2OCl3(O2CPh)2(thf)3] and [NEt4]3[Ti2Cl9]

Abstract

The reaction of [TiCl3(thf)3] with 4 equiv. PhCO2H in refluxing thf or 3 equiv. of Cl– in CH2Cl2 gives [Ti2OCl3(O2CPh)2(thf)3]a and [NEt4]3[Ti2Cl9]2, respectively: crystallography shows them to possess trapped-valence [Ti2(µ-O)(µ-O2CPh)2]3+(TiIIITiIV) and [Ti2(µl)3]3+ cores, respectively, the former with an unusual asymmetrically bridging O2– displaying triple/single bond distances to the metal ions.