Au⋅⋅⋅H−C Hydrogen Bonds as Design Principle in Gold(I) Catalysis

Heidar Darmandeh, Julian Löffler, Nikolaos V. Tzouras, Busra Dereli, Thorsten Scherpf, Kai Stephan Feichtner, Sofie Vanden Broeck, Kristof Van Hecke, Marina Saab, Catherine S.J. Cazin, Luigi Cavallo, Steven P. Nolan*, Viktoria H. Gessner*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

43 Scopus citations

Abstract

Secondary ligand–metal interactions are decisive in many catalytic transformations. While arene–gold interactions have repeatedly been reported as critical structural feature in many high-performance gold catalysts, we herein report that these interactions can also be replaced by Au⋅⋅⋅H−C hydrogen bonds without suffering any reduction in catalytic performance. Systematic experimental and computational studies on a series of ylide-substituted phosphines featuring either a PPh3 (PhYPhos) or PCy3 (CyYPhos) moiety showed that the arene-gold interaction in the aryl-substituted compounds is efficiently compensated by the formation of Au⋅⋅⋅H−C hydrogen bonds. The strongest interaction is found with the C−H moiety next to the onium center, which due to the polarization results in remarkably strong interactions with the shortest Au⋅⋅⋅H−C hydrogen bonds reported to date. Calorimetric studies on the formation of the gold complexes further confirmed that the PhYPhos and CyYPhos ligands form similarly stable complexes. Consequently, both ligands showed the same catalytic performance in the hydroamination, hydrophenoxylation and hydrocarboxylation of alkynes, thus demonstrating that Au⋅⋅⋅H−C hydrogen bonds are equally suited for the generation of highly effective gold catalysts than gold-arene interactions. The generality of this observation was confirmed by a comparative study between a biaryl phosphine ligand and its cyclohexyl-substituted derivative, which again showed identical catalytic performance. These observations clearly support Au⋅⋅⋅H−C hydrogen bonds as fundamental secondary interactions in gold catalysts, thus further increasing the number of design elements that can be used for future catalyst construction.

Original languageEnglish (US)
Pages (from-to)21014-21024
Number of pages11
JournalAngewandte Chemie - International Edition
Volume60
Issue number38
DOIs
StatePublished - Sep 13 2021

Keywords

  • catalysis
  • gold
  • phosphines
  • secondary interactions
  • steric and electronic properties

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry

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