Abstract
The addition of secondary Mes2P(O)H and of bulky tertiary phosphindole oxide onto TiCl4 leads to formation of trans‐[TiCl4(OPR3)2] 1 and 2. Contrary to this finding, Ti(NMe2)4 metalates secondary dimesitylphosphane oxide and mixtures of the mononuclear complexes [Ti(NMe2)4‐n(OPMes2)n] form. The ratio between the amido and phosphinito ligands varies with the stoichiometry, however, pure compounds are not accessible. Fast ligand exchange reactions interconvert these complexes and only mixtures have been obtained. The reaction of TiCl4 with bidentate alkane‐α,ω‐diyl‐bis(diarylphosphane oxides), Ar2P(O)‐(CH2)n‐P(O)Ar2 with Ar/n = Ph/1 (I), Ph/2 (II), Mes/2 (III)) yields insoluble [(I)2Ti2Cl4(µ‐Cl)2] [Ti2Cl9]2 (3), [(II)2TiCl2] [Ti2Cl9]2 (4), and [(III)2(TiCl3)2] [Ti2Cl9]2 (5) regardless of the applied stoichiometry. All these complexes have the dinuclear [Cl3Ti(µ‐Cl)3TiCl3]‐ anion in common.
Published Version
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