Synthesis and structure of new dimeric cyclopentadienyl titanium fluorine-oxygen systems: [Cp*TiF(mu-F)(mu-OPOPh2)](2), [Cp*TiF(mu-F)(mu-OSO2-p-C6H4Me)](2) and [Cp*TiF2(mu-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(mu-F) (mu-OPOPh)(2)](2) 1, [Cp*TiF(mu-F)(mu-OSO2-p-C6H4Me)](2) 2, and [Cp*TiF2(mu-OMe)](2) 3, respe ctively, in good yields. In contrast to the formation of 3, Cp*TiF3 reacts with Al(OH)(3) to afford the known tetramer [Cp*TiF(mu-O)](4) 4. The struct ures of 1-3 have been determined by X-ray crystallography; compounds 1 and 3 crystallize in the monoclinic space group P2(1)/c and compound 2 in the m onoclinic space group P2/n. Compound 1 is the first example of a dimeric Cp *-titanium phosphinate containing a fluorine ligand. The core of the dimeri c structure of both 1 and 2 consists of two Ti atoms bridged by two fluorin e atoms and two bidentate groups. In contrast, the dimeric structure of 3 c onsists of two Ti atoms bridged only by two methoxy groups. An equilibrium of isomers of 1 and 2 has been observed in solution by H-1 and (FNMR)-F-19. The (FNMR)-F-19 spectra of 1-3 are discussed in detail.