Synthesis and Structure of New Dimeric Cyclopentadienyl Titanium Fluorine–Oxygen Systems: [Cp*TiF(μ‐F)(μ‐OPOPh 2 )] 2 , [Cp*TiF(μ‐F)(μ‐OSO 2 ‐ p ‐C 6 H 4 Me)] 2 and [Cp*TiF 2 (μ‐OMe)] 2

The reactions of Cp*TiF 3 with Me 3 SiOPOPh 2 , Me 3 SiOSO 2 ‐ p ‐C 6 H 4 Me, and Al(OMe) 3 resulted in the formation of the dimers [Cp*TiF(μ‐F)(μ‐OPOPh 2 )] 2 1 , [Cp*TiF(μ‐F)(μ‐OSO 2 ‐ p ‐C 6 H 4 Me)] 2 2 , and [Cp*TiF 2 (μ‐OMe)] 2 3 , respectively, in good yields. In contrast to the formation of 3 , Cp*TiF 3 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 P 2 1 /c and compound 2 in the monoclinic space group P 2 /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 1 H and 19 F NMR. The 19 F NMR spectra of 1–3 are discussed in detail.