Non covalent immobilization of pyrene-tagged ruthenium complexes onto graphene surfaces for recycling in olefin metathesis reactions

Houssein Nasrallah (1) , Stéphane Germain (2) , Pierre Queval (2) , Caroline Bouvier (1) , Marc Mauduit (2) , Christophe Crevisy (2) , Emmanuelle Schulz (1)

1 ICMMO - Institut de Chimie Moléculaire et des Matériaux d'Orsay
2 ISCR - Institut des Sciences Chimiques de Rennes

Synthesis of Hoveyda-type ruthenium complexes, modified by pyrene tags on the NHC ligand and/or the benzylidene moiety, is described. Thanks to non-covalent it-err interactions these new complexes were immobilized on carbon supports [reduced graphene oxide (rGO) or graphene] and their activity and recoverability for metatheses reactions have been studied. A SIPr-based complex possessing the pyrene function on the benzylidene ligand (C2) delivered the best results for the ring closing metathesis of diethyldiallyl malonate as benchmark reaction. The presence of additional pyrene-functionalized styrenyl-ether as ligand to the rGO-supported catalyst (C2/L@rGO) noticeably improved the recycling procedure allowing supplementary efficient catalytic runs. This may be due either to a facilitated boomerang effect or to a gradual release of the active species in solution. Finally, catalyst C2/L@rGO was proven to be successfully used to promote metathesis reactions in a multisubstrate procedure, the same supported catalyst batch being successively engaged to transform three different substrates, in diene and ene-yne RCM reactions.

Keywords: n-heterocyclic carbene; pi-stacking interactions; ring-closing metathesis; carbon nanotubes; metal-complexes; grubbs-hoveyda; ionic liquids; ru carbene; catalysts; mechanism

Domains: Chemical Sciences; Chemical Sciences; Catalysis; Chemical Sciences; Material chemistry

Houssein Nasrallah, Stéphane Germain, Pierre Queval, Caroline Bouvier, Marc Mauduit, et al.. Non covalent immobilization of pyrene-tagged ruthenium complexes onto graphene surfaces for recycling in olefin metathesis reactions. Journal of Molecular Catalysis A: Chemical, 2016, 425, pp.136--146. ⟨10.1016/j.molcata.2016.10.004⟩. ⟨hal-01475469⟩