A Well-Defined Pd Hybrid Material for the Z-Selective Semihydrogenation of Alkynes Characterized at the Molecular Level by DNP SENS.

Matthew P Conley (1) , Ruben M Drost (2) , Mathieu Baffert (3) , David Gajan (1) , Cornelis Elsevier (2) , W Trent Franks (4) , Hartmut Oschkinat (4) , Laurent Veyre (3) , Alexandre Zagdoun (5) , Aaron J. Rossini (6) , Moreno Lelli (6) , Anne Lesage (6) , Gilles Casano (7) , Olivier Ouari (7) , Paul Tordo (7) , Lyndon Emsley (6) , Christophe Copéret (1) , Chloé Thieuleux (3)

1 Laboratory of Inorganic Chemistry
2 van ‘t Hoff Institute for Molecular Sciences
3 C2P2 - Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265
4 FMP - Leibniz Forschungsinstitut für Molekulare Pharmakolgie = Leibniz Institute for Molecular Pharmacology [Berlin, Allemagne]
5 ISA - Institut des Sciences Analytiques
6 ISA - Centre de RMN à très hauts champs
7 ICR - Institut de Chimie Radicalaire

Direct evidence of the conformation of a Pd-N heterocyclic carbene (NHC) moiety imbedded in a hybrid material and of the Pd-NHC bond were obtained by dynamic nuclear polarization surface-enhanced NMR spectroscopy (DNP SENS) at natural abundance in short experimental times (hours). Overall, this silica-based hybrid material containing well-defined Pd-NHC sites in a uniform environment displays high activity and selectivity in the semihydrogenation of alkynes into Z-alkenes.

Mots clés: carbenes; hybrid materials; palladium; NMR spectroscopy; semihydrogenation; DYNAMIC NUCLEAR-POLARIZATION; ENHANCED NMR-SPECTROSCOPY; N-HETEROCYCLIC CARBENE; SURFACE ORGANOMETALLIC CHEMISTRY; HETEROGENEOUS CATALYSTS; HYDROGENATION CATALYSTS; ALKENE METATHESIS; FORMIC-ACID; NHC; COMPLEX

Domaines: Chimie analytique; Chimie théorique et/ou physique

Matthew P Conley, Ruben M Drost, Mathieu Baffert, David Gajan, Cornelis Elsevier, et al.. A Well-Defined Pd Hybrid Material for the Z-Selective Semihydrogenation of Alkynes Characterized at the Molecular Level by DNP SENS.. Chemistry - A European Journal, 2013, 19 (37), pp.12234-12238. ⟨10.1002/chem.201302484⟩. ⟨hal-00864651⟩