Pd/S cooperativity: from stoichiometric activation of Si−H bonds to catalytic hydrosilylation
Abstract With the aim to explore metal‐ligand cooperation across Pd−S linkages, we designed a quinoline‐based PNS tridentate ligand and prepared Pd(II) complexes thereof. Optimal solubility and stability of the dicationic complex [(PNS)Pd(II)] 2 2+ IV 2 were achieved with B(C 6 F 5 ) 4 – as counter‐anion. It adopts a thiolate‐bridged dimeric structure with a (PdS) 2 core, but readily activates hydrosilanes across the Pd−S linkage. The resulting mononuclear Pd(II) hydride [(PNS SiR3 )Pd(II)H] + VI was characterized by multi‐nuclear NMR spectroscopy and the Si−H bond coordination/activation was studied computationally. Complex IV 2 was found to efficiently catalyze the hydrosilylation of alkynes, internal as well as terminal, with good stereo and regioselectivity.
Authors
- Julien Monot (ORCID: https://orcid.org/0000-0001-9969-2876)
- Arnaud Clerc (ORCID: https://orcid.org/0000-0003-0875-968X)
- Sonia Mallet‐Ladeira (ORCID: https://orcid.org/0009-0004-2446-6697)
- M. Humbert
- Didier Bourissou (ORCID: https://orcid.org/0000-0002-0249-1769)
- Blanca M. Martín-Vaca (ORCID: https://orcid.org/0000-0002-3822-0645)
- Karinne Miqueu
Institutions
- Centre National de la Recherche Scientifique (FR)
- Université Toulouse III - Paul Sabatier (FR)
- Institut des Sciences Analytiques et de Physico-Chimie pour l'Environnement et les Matériaux (FR)
- Institut de Chimie (FR)
- Laboratoire Hétérochimie Fondamentale et Appliquée (FR)
Publication Details
- Journal
- ChemistryEurope
- Published
- 2024-11-12
- DOI
- https://doi.org/10.1002/ceur.202400079
- Citations
- 1
- Primary Topic
- Organoboron and organosilicon chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.25
Funders
- Ministère de l'Enseignement supérieur, de la Recherche et de l'Innovation
- Agence Nationale de la Recherche
- Université de Toulouse
- Centre National de la Recherche Scientifique