Spectroscopic Manifestations and Implications for Catalysis of Quasi-d10 Configurations in Formal Gold(III) Complexes.

Evgeniya A Trifonova, Isaac F Leach, Winfried B de Haas, Remco W A Havenith, Moniek Tromp*, Johannes E M N Klein*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

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Several gold +I and +III complexes are investigated computationally and spectroscopically, focusing on the d-configuration and physical oxidation state of the metal center. Density functional theory calculations reveal the non-negligible electron-sharing covalent character of the metal-to-ligand σ-bonding framework. The bonding of gold(III) is shown to be isoelectronic to the formal CuIII complex [Cu(CF3)4]1- , in which the metal center tries to populate its formally unoccupied 3dx2-y2 orbital via σ-bonding, leading to a reduced d10 CuI description. However, Au L3-edge X-ray absorption spectroscopy reveals excitation into the d-orbital of the AuIII species is still possible, showing that a genuine d10 configuration is not achieved. We also find an increased electron-sharing nature of the σ-bonds in the AuI species, relative to their AgI and CuI analogues, due to the low-lying 6s orbital. We propose that gold +I and +III complexes form similar bonds with substrates, owing primarily to participation of the 5dx2-y2 or 6s orbital, respectively, in bonding, indicating why AuI and AuIII complexes often have similar reactivity.

Original languageEnglish
Article numbere202215523
Number of pages8
JournalAngewandte Chemie (International ed. in English)
Issue number3
Publication statusPublished - 16-Jan-2023


  • Catalysis
  • Computational Chemistry
  • Covalent Bonding
  • Gold
  • Oxidation States

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