Titanium tetrafluoride complexation with phosphorylated ketone Ph2P(O)(CH2)2C(O)Me in CH2Cl2

The products resulting from the reaction of TiF4 with Ph2P(O)(CH2)2C(O)Me (L') in CH2Cl2 have been studied by 19F{1H} and 31P{1H} NMR spectroscopy. At a twofold excess of L', solution contains cis-TiF4(L')2 (>90%), trans-TiF4(L')2, and fac-[TiF3L3']+, where L' is coordinated via the P=O group, as well as the dimer [(Ti2F7L'2)2]+, where L' is coordinated through the P=O and C=O groups. An equimolar solution contains dimeric and polynuclear complexes containing moieties with three terminal cis fluorine ions, while the other coordination sites are occupied by the P=O groups and F– bridges. At a twofold excess of TiF4, ligand L' coordinates via the P=O and C=O groups and behaves as a bridge along with F– ions. Thermodynamic stability of the structures of the TiF4L'2 isomers and the structure of [(µ-F)(µ-L')2(TiF3)2]+ has been calculated.