Au–Mn Bond Formal Metathesis with Ar–F via Synergistic Bimetallic Activation

Selective C–F activation with gold-complex has been esteemed as a long-standing issue owing to a kinetically unfavorable oxidative addition elementary reaction. Herein, we report a synergistic bimetallic Au–Mn bond formal metathesis with aromatic C(sp 2 )–F bond, establishing a versatile platform for the synthesis of polyfluorophenyl-substituted Au(I) complexes. A wide range of structurally diverse L–Au(I)–Ar Fn complexes (37 examples, up to 98% yield) have been readily constructed. Mechanistic studies together with DFT calculations support that the key C–F bond cleavage proceeds via thermodynamically and kinetically feasible Au–Mn bimetallic cooperative activation, rather than direct oxidative addition toward either Au or Mn metal center. Notably, these aryl gold(I) complexes exhibit broad biological functions, including anticancer and/or anti-inflammatory efficacy, facilitating promising candidate drug discovery for pharmaceutical development. This bimetallic strategy should open new avenues to achieve unique reactivity profiles and novel mechanistic pathways.