Perfluorinated Ligands in Organometallic Chemistry

New coordination modes for octafluorocyclooctatetraene OFCOT bound to rhodium, cobalt, nickel, palladium, platinum and manganese have been discovered. All complexes show good air and thermal stability compared to hydrocarbon analogues. Photochemical rearrangements of cobalt and rhodium OFCOT complexes, and unprecedented transannular ring closure chemistry have been discovered. Comparison of the bonding properties of OFCOT with those of its hydrocarbon analogue has been achieved using crystallographic and NMR studies. The first examples of a new family of trialkyltricarbonyl organometallic compounds, stabilized by tridentate perfluorinated ligands. Dinuclear rhodium complexes of OFCOT undergo a selective C-F bond activation reaction. Electrochemical reduction of OFCOT bound to cobalt yields the first example of a fluorinated organometallic radical anion. Metal substitution on the OFCOT ring has been achieved, and vicinal defluorination of OFCOT gives a series of compounds containing the previously unknown mu-hexafluorocyclooctatrieneyne ligand. Stereospecific cleavage of a fluorinated C-C bond sigma-bond in perfluorocyclopropene by platinum and iridium complexes has been achieved.