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Au...H-C hydrogen bonds as design principle in gold(I) catalysis

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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 ((Ph)YPhos) or PCy3 ((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.
Keywords
catalysis, gold, phosphines, secondary interactions, steric and electronic properties, CENTER-DOT-AU, COMPLEXES, PHOSPHINES, SILVER, CYCLOADDITIONS, LIGANDS, METALS, ATOMS

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MLA
Darmandeh, Heidar, et al. “Au...H-C Hydrogen Bonds as Design Principle in Gold(I) Catalysis.” ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, vol. 60, no. 38, 2021, pp. 21014–24, doi:10.1002/anie.202108581.
APA
Darmandeh, H., Loeffler, J., Tzouras, N., Dereli, B., Scherpf, T., Feichtner, K.-S., … Gessner, V. H. (2021). Au...H-C hydrogen bonds as design principle in gold(I) catalysis. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 60(38), 21014–21024. https://doi.org/10.1002/anie.202108581
Chicago author-date
Darmandeh, Heidar, Julian Loeffler, Nikolaos Tzouras, Busra Dereli, Thorsten Scherpf, Kai-Stephan Feichtner, Sofie Vanden Broeck, et al. 2021. “Au...H-C Hydrogen Bonds as Design Principle in Gold(I) Catalysis.” ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 60 (38): 21014–24. https://doi.org/10.1002/anie.202108581.
Chicago author-date (all authors)
Darmandeh, Heidar, Julian Loeffler, Nikolaos Tzouras, Busra Dereli, Thorsten Scherpf, Kai-Stephan Feichtner, Sofie Vanden Broeck, Kristof Van Hecke, Marina Saab, Catherine Cazin, Luigi Cavallo, Steven Nolan, and Viktoria H. Gessner. 2021. “Au...H-C Hydrogen Bonds as Design Principle in Gold(I) Catalysis.” ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 60 (38): 21014–21024. doi:10.1002/anie.202108581.
Vancouver
1.
Darmandeh H, Loeffler J, Tzouras N, Dereli B, Scherpf T, Feichtner K-S, et al. Au...H-C hydrogen bonds as design principle in gold(I) catalysis. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION. 2021;60(38):21014–24.
IEEE
[1]
H. Darmandeh et al., “Au...H-C hydrogen bonds as design principle in gold(I) catalysis,” ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, vol. 60, no. 38, pp. 21014–21024, 2021.
@article{8720175,
  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 ((Ph)YPhos) or PCy3 ((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.}},
  author       = {{Darmandeh, Heidar and Loeffler, Julian and Tzouras, Nikolaos and Dereli, Busra and Scherpf, Thorsten and Feichtner, Kai-Stephan and Vanden Broeck, Sofie and Van Hecke, Kristof and Saab, Marina and Cazin, Catherine and Cavallo, Luigi and Nolan, Steven and Gessner, Viktoria H.}},
  issn         = {{1433-7851}},
  journal      = {{ANGEWANDTE CHEMIE-INTERNATIONAL EDITION}},
  keywords     = {{catalysis,gold,phosphines,secondary interactions,steric and electronic properties,CENTER-DOT-AU,COMPLEXES,PHOSPHINES,SILVER,CYCLOADDITIONS,LIGANDS,METALS,ATOMS}},
  language     = {{eng}},
  number       = {{38}},
  pages        = {{21014--21024}},
  title        = {{Au...H-C hydrogen bonds as design principle in gold(I) catalysis}},
  url          = {{http://dx.doi.org/10.1002/anie.202108581}},
  volume       = {{60}},
  year         = {{2021}},
}

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