Intramolecular Rearrangement for Regioselective Complexation by Intramolecular CH/pi Interaction in a Hydrophobic Cavity of a Ruthenium Coordination Sphere

摘要

A Ru~(II)complex with a hy-drophobic cavity formed from two 1-naphthoylamide groups was prepared.Its reactions with beta-diketones gave beta-diketonato complexes in which hydro-phobic pi-pi or CH/pi interactions were confirmed by NMR spectroscopy and X-ray crystallography.In the case of the asymmetric beta-diketone benzoylace-tone,an isomer with a CH/Jt interaction was afforded as the sole product owing to thermodynamic control.The reaction was found to involve a novel intramolecular rearrangement from the phenyl-included isomer to the methyl-included one without rupture of Ru-(3-diketonato coordination bonds(activation energy 52kJmol~(-1)).This indicates that CH/it interactions can be more favored thermodynamically than pi-pi interactions in a suitable hydrophobic environment.