Hydrogenation Versus Hydrosilylation: The Substantial Impact of a Palladium Capsule on the Catalytic Outcome
Maxime Steinmetz1, Rachel Schurhammer2, Christophe Gourlaouen2
1Synthèse Organométallique et Catalyse, UMR-CNRS 7177, Institut de Chimie de Strasbourg, Strasbourg University, 67008 Strasbourg, France.
Abstract:
A palladium capsule, made of three cavitands, namely P,P-dichlorido{5,17-bis[5-(diphenylphosphanyl)-4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]arenyl-17-oxymthyl]-4(24),6(10),12(16),18(22)-tetramethylenedioxy-2,8,14,20-tetrapentylresorcin[4]arene}palladium(II) (1), was synthetized by coordination of the corresponding diphosphinated ligand and the palladium precursor [PdCl2(PhCN)2] in 27% yield. The obtained P,P-chelate complex was fully characterized by elemental analysis, NMR and mass spectrometry. Molecular dynamics simulations carried out on the metallo-capsule showed the structure made by the three cavitands was slightly distorted over the 1 μs of the simulation. The evaluation of the palladium capsule 1 in the reaction between arylacetylenes and Et3SiH in undried conditions unequivocally demonstrates a drastic change in chemoselectivity, with the formation of the partially hydrogenation product rather than the hydrosilylation products observed with complexes whose active center is more accessible, for instance [PdCl2(PPh3)2].
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