SYNTHESIS, STRUCTURE, AND REACTIVITY OF CHIRAL RHENIUM N-PYRROLYL COMPLEXES [(ETA(5)-C5H5)RE(NO)(PPH(3))(NCR=CR'CH=CH)] - REGIOCHEMISTRY OF ELECTROPHILIC ADDITION AND UNPRECEDENTED REARRANGEMENTS TO CARBON-LIGATED SPECIES
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abstract
Enhanced reactivity of the Npyrrolyl ligand in complex 1, compared to free pyrrole, is observed in aromatic electrophilic substitutions. Complex 1 and TfOH or HBF4.OEt2 give isolable 2Hpyrrole complexes, which undergo unprecedented rearrangements to the carbonligated species (see below). Possible mechanisms, crystallographic and Hckel MO data, and potential applications of this chemistry are discussed. (Figure Presented.)