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<p>Radical ligand transfer (RLT), a process in which alkyl radicals capture ligands from high-valent metal species, has emerged as a powerful synthetic approach in organic chemistry. While RLT processes mediated by 3<i>d</i> transition metals have been developed, the application of 5<i>d</i> transition metals remains underexplored due to the limited flexibility in their oxidation states. Here we present a catalytic approach leveraging sequential photoinduced electron transfer in dinuclear gold complexes to achieve an efficient RLT process. This strategy facilitates formal additions of <i>gem</i>-dichloroalkanes and Freon-22 bearing unactivated C(<i>sp</i><sup>3</sup>)–Cl bonds to different kinds of alkenes, with high reactivity, excellent atom economy and broad scope. Combined mechanistic and theoretical investigations reveal a latent Au<sup>II</sup>Au<sup>II</sup> pathway. The success originates from sequential excitation of dinuclear gold complexes for the formation of a covalent Au–Au bond, which can markedly weaken the Au–Cl bond and facilitate ligand transfer.</p><p></p>

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Radical ligand transfer catalysis of photoexcited dinuclear gold complexes

  • 期刊论文

  • 发表日期：

    2026年1月6日

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  • Yaohang Cheng,
  • Chengyihan Gu,
  • Jie Han,
  • Yulan Chen,
  • Yuxi Tian,
  • Chengjian Zhu,
  • Jin Xie

摘要

Radical ligand transfer (RLT), a process in which alkyl radicals capture ligands from high-valent metal species, has emerged as a powerful synthetic approach in organic chemistry. While RLT processes mediated by 3d transition metals have been developed, the application of 5d transition metals remains underexplored due to the limited flexibility in their oxidation states. Here we present a catalytic approach leveraging sequential photoinduced electron transfer in dinuclear gold complexes to achieve an efficient RLT process. This strategy facilitates formal additions of gem-dichloroalkanes and Freon-22 bearing unactivated C(sp3)–Cl bonds to different kinds of alkenes, with high reactivity, excellent atom economy and broad scope. Combined mechanistic and theoretical investigations reveal a latent AuIIAuII pathway. The success originates from sequential excitation of dinuclear gold complexes for the formation of a covalent Au–Au bond, which can markedly weaken the Au–Cl bond and facilitate ligand transfer.