Anti-Markovnikov Hydroarylation of Unactivated Olefins Catalyzed by a Bis-tropolonato Iridium(III) Organometallic Complex

Recently, we reported the first catalytic, intermolecular, anti-Markovnikov hydroarylation of unactivated olefins by a homogeneous, bis-chelating, O-donor Ir(III) complex, (acac-O,O)_2Ir(R)(L), based on the simplest β-diketonate acetylacetonate (acac-O,O). With the ultimate objective of designing more active catalysts for this potentially useful reaction on the basis of structure function studies, we synthesized the related O-donor, bis-tropolonato Ir(III) organometallic analogues. Herein, we report that the new O-donor complex, (trop-O,O)_2Ir(Ph)(Py), is an active catalyst for the anti-Markovnikov hydroarylation of unactivated olefins and that theoretical calculations are consistent with catalysis proceeding via arene CH activation and olefin insertion.