Competition between vinylidene rearrangement and 1,2-insertion of carbon-disubstituted internal alkynes at a Cp∗Ir(III) complex

Abstract

Competition between vinylidene rearrangement/1,1-insertion and 1,2-alkyne insertion into the Ir-Ar bond of [Cp∗Ir(ppy-F4)]+ was observed on reaction with diarylacetylenes. The former process afforded the iridacycle 2via the subsequent 1,4-Ir migration, whereas the latter led to the pyridoisoquinolinium complex 4. Detailed analysis revealed that 4 isomerizes to 2 by heating at 50 °C.