Abstract
AbstractThe reaction of iPrPCPIr with diphenylacetylene (iPrPCP=κ3‐2,6‐C6H3(CH2P(iPr)2)2), generated by dehydrogenation of iPrPCPIrH4 with tert‐butylethylene, readily provides the π‐adduct iPrPCPIr(η2‐PhC≡CPh) in quantitative yield at room temperature. Heating solutions of iPrPCPIr(η2‐PhC≡CPh) in aromatic hydrocarbon solvents leads to isomerization forming the 1‐iridaindene iPrPCPIr(C8H5(2‐Ph)). Surprisingly, this seemingly intramolecular reaction presents a kinetic isotope effect of 4.6 in C6H6 versus C6D6 solvent. The rate of this isomerization is effected by the availability of easily activated C−H bonds (i. e. aromatic C(sp2)‐H without ortho‐substituents), and is strongly dependent upon the ratio of C−H to C−D bonds. Experiments indicate that many, or all, of the steps in this process may be reversible and that a highly fluxional C−H/D addition product is present during isomerization.
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