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44147-AC3
Transition Metal-Templated Reduction of Carbon-Fluorine Bonds: A New General Route to Unsaturated Fluorocarbon Ligands

Russell P. Hughes, Dartmouth College

Considerable progress has been made in the past year on elaborating our preliminary observations, which showed that sphaerointraneous reduction of primary perfluoroalkyl-iridium complexes leads to a clean route to the first examples pf perfluoroalkylidene complexes. We have now found that these Ir=C double bonds are easily isomerized from cis to trans under fluorescent light conditions; the photostationary state responsible for this easy isomerization is under investigation experimentally and computationally. Addition of hydrogen chloride to these iridium-fluoroalkylidene bonds has been found to occur both regio- and stereospecifically. The first examples of bis(perfluoroalkyl) carbene compounds have now been isolated and characterized. Further reduction in the coordination sphere affords clean routes to perfluoroallene and perfluoro-2-butyne complexes.

Further experimental and computational studies are underway, and a number of manuscripts describing this work are either in review or in preparation.

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