@article{Poier:15376,
      recid = {15376},
      author = {Poier, Dario and Loveday, Oliver and Usteri, Marc Eduard  and Stoian, Dragos and López, Núria and Mitchell, Sharon  and Marti, Roger and Pérez-Ramírez, Javier},
      title = {Ligand-induced activation of single-atom palladium  heterogeneous catalysts for cross-coupling reactions},
      publisher = {American Chemical Society (ACS)},
      journal = {ACS Nano},
      address = {Washington, DC, USA. 2025-01},
      number = {ARTICLE},
      pages = {9 p.},
      abstract = {Single-atom heterogeneous catalysts (SACs) are potential,  recoverable alternatives to soluble organometallic  complexes for cross-coupling reactions in fine-chemical  synthesis. When developing SACs for these applications, it  is often expected that the need for ligands, which are  essential for organometallic catalysts, can be bypassed.  Contrary to that, ligands remain almost always required for  palladium atoms stabilized on commonly used functionalized  carbon and carbon nitride supports, as the catalysts  otherwise show limited activity. Despite this, ligand  optimization has received little attention, and their role  in activating SACs is poorly understood. Here, we explore  the impact of structurally diverse phosphine ligands on the  performance of nitrogen-doped carbon supported single-atoms  (Pd1@NC) in the Sonogashira–Hagihara (SH) cross-coupling  reaction, using X-ray absorption spectroscopy and density  functional theory simulations to rationalize the observed  trends. Compared to the ligand-free SAC, SH activity is  enhanced in almost all ligand-assisted systems, with  reactivity varying by up to 8 orders of magnitude depending  on the ligand choice. Distinct trends emerge based on the  free ligand volume and ligand class. Unlike molecular  systems, the electronic effects of phosphine ligands are  less significant in SACs due to the modulating influence of  the support. Instead, the performance of SAC-ligand systems  is governed by a balance between the ligand deformation  energy during coordination with metal centers, and their  resulting accessibility to cross-coupling reagents. These  findings offer key insights into optimizing Pd-SACs by  leveraging phosphine ligands to activate metal centers and  tailor the 3D environment.},
      url = {http://arodes.hes-so.ch/record/15376},
      doi = {https://doi.org/10.1021/acsnano.4c14131},
}