Synthesis and Structure of New Dimeric Cyclopentadienyl Titanium Fluorine–Oxygen Systems: [Cp*TiF(μ‐F)(μ‐OPOPh2)]2, [Cp*TiF(μ‐F)(μ‐OSO2‐p‐C6H4Me)]2 and [Cp*TiF2(μ‐OMe)]2

The reactions of Cp*TiF3 with Me3SiOPOPh2, Me3SiOSO2‐p‐C6H4Me, and Al(OMe)3 resulted in the formation of the dimers [Cp*TiF(μ‐F)(μ‐OPOPh2)]2 1, [Cp*TiF(μ‐F)(μ‐OSO2‐p‐C6H4Me)]2 2, and [Cp*TiF2(μ‐OMe)]2 3, respectively, in good yields. In contrast to the formation of 3, Cp*TiF3 reacts with Al(OH)3 to afford the known tetramer [Cp*TiF(μ‐O)]4 4. The structures of 1–3 have been determined by X‐ray crystallography; compounds 1 and 3 crystallize in the monoclinic space group P21/c and compound 2 in the monoclinic space group P2/n. Compound 1 is the first example of a dimeric Cp*‐titanium phosphinate containing a fluorine ligand. The core of the dimeric structure of both 1 and 2 consists of two Ti atoms bridged by two fluorine atoms and two bidentate groups. In contrast, the dimeric structure of 3 consists of two Ti atoms bridged only by two methoxy groups. An equilibrium of isomers of 1 and 2 has been observed in solution by 1H and 19F NMR. The 19F NMR spectra of 1–3 are discussed in detail.