Reaction of the fluoroolefin-bridged complexes, [Ir2(CH3)(CO)2(�-olefin)(dppm)2]+ (dppm = Ph2PCH2PPh2; olefin =  F2C=CH2, F2C=CHF, F2C=CF2),  with trimethylsilyl triflate or triflic acid at sub-ambient temperatures results in facile fluoride-ion abstraction of one of the geminal fluorines to give the corresponding fluorovinyl products. A second fluoride can also be removed to yield the corresponding vinylidene or fluorovinylidene species. With trifluoroethylene, fluoride abstraction can also be effected by water � although in this case the lone vicinal fluorine is removed to give an unusual coordination mode for the resulting 2,2-difluorovinyl group. Reaction of the fluorovinyl-containing complexes with hydrogen results in hydrogenolysis, converting tetrafluoroethylene to trifluoroethylene, which can in turn be converted to cis-difluoroethylene. Under similar conditions, 1,1-difluoroethylene is converted to fluoroethylene. Reaction of the cis-difluorovinyl-bridged complex, [Ir2(CH3)(OTf)(CO)2(�-CF=CHF)(dppm)2]+, with CO yields two isomers of difluoropropene. Reaction of the 1-fluorovinyl analogue with water yields 2-fluoropropene. These and other results will be discussed.

Carbon–fluorine bond activation in fluoroolefins promoted by adjacent metals

239th National Meeting (2010)

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