An Arbuzov-type reaction with the bis(alkynyl) iridium complex [Cp*Ir(L)(C[tbnd]CAr)2

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Abstract The bis(alkynyl) iridium complexes [Cp*Ir(L)(C CAr) 2 ] undergo an Arbuzov-type reaction with phosphites to give four-membered iridacyclic phosphonates [Cp*Ir(L){C(Ar) C[P( O)(OR) 2 ]C CHAr}]. These can isomerise to a five-membered iridafuran in the presence of a strong acid. In the absence of a phosphite, the bis(alkynyl) iridium complexes undergo acid-catalysed aerobic oxidation to form 1,2-diketone iridabenzofurans [Cp*Ir(L){C 6 H 4 - 1,2 -CH CC( O)C( O)Ar}]. A common reaction pathway involving initial protonation and alkynyl migration is proposed.