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

Siyu Xia,Weina Zhong,Tin Y. Li,Zhongren Xu,Jie Han,Wukun Liu,Weipeng Li,Chengjian Zhu,Jin Xie

Published 2025 in Journal of the American Chemical Society

ABSTRACT

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(sp2)-F bond, establishing a versatile platform for the synthesis of polyfluorophenyl-substituted Au(I) complexes. A wide range of structurally diverse L-Au(I)-ArFn 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.

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