Synthesis and structural characterization of sulfonates, phosphinates and carboxylates of organometallic Group 4 metal fluorides

Reaction of [Cp^*TiF₃] (Cp^* = (ν⁵-C₅Me₅)) with Me₃SiOSO₂- p-C₆H₄CH₃, Me₃SiOPOPh₂ and 1,2-(Me₃SiOCO)₂C₆H₄ yields the dinuclear complexes [{Cp^*TiF(μ-F)(μ-OSO₂-p-C₆H₄CH₄)}₂] (1), [{Cp^*TiF(μ-F)(μ-OPOPh₂)}₂] (2) and [{Cp^*TiF(μ-F)(μ-OCO-o-C₆H₄CO₂SiMe₃)}₂] (3). The molecular structures of 1 and 2 have been determined by single-crystal X-ray analysis. In complexes 1-3, the two titanium atoms are connected by bridging fluorine atoms as well as bridging sulfonate, phosphinate and carboxylate groups respectively. Each titanium atom is also bonded to a terminal fluorine atom. Reaction of [Cp₂^*ZrF₂] with 1,2-(Me₃SiOCO)₂C₆H₄ leads to the mononuclear pentacoordinate 18-electron species [Cp₂^*ZrF(μ-OCO-o-C₆H₄CO₂SiMe₃)] (4) and its structure was determined by X-ray crystallographic methods.