σ‐Cyclopropyl to π‐Allyl Rearrangement at Au(III)

The possibility for Au(III) σ-cyclopropyl complexes to undergo ring-opening and give π-allyl was interrogated. transformation first evidenced within (P,C)-cyclometalated complexes, it occurs hours at –50°C. It then generalized other ancillary ligands. With (N,C)-cyclometalated the rearrangement room temperature while proceeds already –80°C with a dicationic (P,N)-chelated complex. Density Functional Theory (DFT) calculations shed light on mechanism of transformation, disrotatory electrocyclic ring-opening. Intrinsic Bond Orbital (IBO) analysis along reaction profile shows cleavage distal σ(CC) bond π-bonded allyl moiety. Careful inspection structure bonding cationic support possible existence C–C agostic interactions Au(III).