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)]22+ IV2 were achieved with B(C6F5)4– as counter‐anion. It...
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| Format: | Article |
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Wiley-VCH
2025-01-01
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| Series: | ChemistryEurope |
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| Online Access: | https://doi.org/10.1002/ceur.202400079 |
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| author | Arnaud Clerc Marceline Humbert Sonia Mallet‐Ladeira Dr. Karinne Miqueu Dr. Julien Monot Prof. Blanca Martín‐Vaca Dr. Didier Bourissou |
| author_facet | Arnaud Clerc Marceline Humbert Sonia Mallet‐Ladeira Dr. Karinne Miqueu Dr. Julien Monot Prof. Blanca Martín‐Vaca Dr. Didier Bourissou |
| author_sort | Arnaud Clerc |
| collection | DOAJ |
| description | 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)]22+ IV2 were achieved with B(C6F5)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 [(PNSSiR3)Pd(II)H]+ VI was characterized by multi‐nuclear NMR spectroscopy and the Si−H bond coordination/activation was studied computationally. Complex IV2 was found to efficiently catalyze the hydrosilylation of alkynes, internal as well as terminal, with good stereo and regioselectivity. |
| format | Article |
| id | doaj-art-24791b26b7bd4c1597ee4f8de26fd645 |
| institution | Kabale University |
| issn | 2751-4765 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemistryEurope |
| spelling | doaj-art-24791b26b7bd4c1597ee4f8de26fd6452025-01-13T07:31:32ZengWiley-VCHChemistryEurope2751-47652025-01-0131n/an/a10.1002/ceur.202400079Pd/S cooperativity: from stoichiometric activation of Si−H bonds to catalytic hydrosilylationArnaud Clerc0Marceline Humbert1Sonia Mallet‐Ladeira2Dr. Karinne Miqueu3Dr. Julien Monot4Prof. Blanca Martín‐Vaca5Dr. Didier Bourissou6Laboratoire Hétérochimie Fondamentale et Appliquée (LHFA, UMR 5069) CNRS/Université Paul Sabatier 118 Route de Narbonne 31062 Toulouse Cedex 09 FranceLaboratoire Hétérochimie Fondamentale et Appliquée (LHFA, UMR 5069) CNRS/Université Paul Sabatier 118 Route de Narbonne 31062 Toulouse Cedex 09 FranceInstitut de Chimie de Toulouse (FR2599) 118 Route de Narbonne 31062 Toulouse Cedex 09 FranceCNRS/Université de Pau et des Pays de l'Adour E2S-UPPA Institut des Sciences Analytiques et Physico-Chimie pour l'Environnement et les Matériaux (IPREM, UMR 5254) Hélioparc, 2 Avenue du Président Angot 64053 Pau Cedex 09 FranceLaboratoire Hétérochimie Fondamentale et Appliquée (LHFA, UMR 5069) CNRS/Université Paul Sabatier 118 Route de Narbonne 31062 Toulouse Cedex 09 FranceLaboratoire Hétérochimie Fondamentale et Appliquée (LHFA, UMR 5069) CNRS/Université Paul Sabatier 118 Route de Narbonne 31062 Toulouse Cedex 09 FranceLaboratoire Hétérochimie Fondamentale et Appliquée (LHFA, UMR 5069) CNRS/Université Paul Sabatier 118 Route de Narbonne 31062 Toulouse Cedex 09 FranceAbstract 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)]22+ IV2 were achieved with B(C6F5)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 [(PNSSiR3)Pd(II)H]+ VI was characterized by multi‐nuclear NMR spectroscopy and the Si−H bond coordination/activation was studied computationally. Complex IV2 was found to efficiently catalyze the hydrosilylation of alkynes, internal as well as terminal, with good stereo and regioselectivity.https://doi.org/10.1002/ceur.202400079Homogeneous catalysisHydrosilylationMetal/ligand cooperationPalladiumPincer ligandSulfur |
| spellingShingle | Arnaud Clerc Marceline Humbert Sonia Mallet‐Ladeira Dr. Karinne Miqueu Dr. Julien Monot Prof. Blanca Martín‐Vaca Dr. Didier Bourissou Pd/S cooperativity: from stoichiometric activation of Si−H bonds to catalytic hydrosilylation ChemistryEurope Homogeneous catalysis Hydrosilylation Metal/ligand cooperation Palladium Pincer ligand Sulfur |
| title | Pd/S cooperativity: from stoichiometric activation of Si−H bonds to catalytic hydrosilylation |
| title_full | Pd/S cooperativity: from stoichiometric activation of Si−H bonds to catalytic hydrosilylation |
| title_fullStr | Pd/S cooperativity: from stoichiometric activation of Si−H bonds to catalytic hydrosilylation |
| title_full_unstemmed | Pd/S cooperativity: from stoichiometric activation of Si−H bonds to catalytic hydrosilylation |
| title_short | Pd/S cooperativity: from stoichiometric activation of Si−H bonds to catalytic hydrosilylation |
| title_sort | pd s cooperativity from stoichiometric activation of si h bonds to catalytic hydrosilylation |
| topic | Homogeneous catalysis Hydrosilylation Metal/ligand cooperation Palladium Pincer ligand Sulfur |
| url | https://doi.org/10.1002/ceur.202400079 |
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