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. Däschlein-Gessner

Research output: Contribution to journalArticlepeer-review


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 PPh 3 ( Ph YPhos) or PCy 3 ( Cy YPhos) 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 Ph YPhos and Cy YPhos 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)
JournalAngewandte Chemie
StatePublished - Jul 27 2021

Bibliographical note

KAUST Repository Item: Exported on 2021-07-29
Acknowledgements: This work was supported by RESOLV, funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany's Excellence Strategy – EXC-2033 -Projektnummer 390677874 and by the European Research Council (Starting Grant: YlideLigands 677749). We also gratefully acknowledge VLAIO (SBO project CO2PERATE), for support. The Special Research Fund (BOF) of Ghent University
is also acknowledged (starting and advanced grants to SPN). The Research Foundation – Flanders (FWO) is thanked for PhD fellowships to N.V.T (11I6921N) and S.V.B (1S99819N). KVH and MS thank the Research Foundation – Flanders (FWO) (project AUGE/11/029) and the Special Research Fund (BOF) –UGent (project 01N03217) for funding. Umicore AG is acknowledged for generous gifts of materials.

ASJC Scopus subject areas

  • Medicine(all)


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