title: Outer-Sphere Reactivity Shift of Secondary Phosphine Oxide-Based Nickel Complexes: From Ethylene Hydrophosphinylation to Oligomerization.
abstract: A new dimension for secondary phosphine oxide (SPOs) ligands is described in this article. Demonstrated on original π-allylic nickel structures, these self-assembled complexes trigger catalytic hydrophosphinylation reactions. Addition of a Lewis acid B(C6F5)3switches the reactivity towards migratory insertion and thus ethylene oligomerization through an unprecedented outer-sphere interaction with the coordinated SPO ligand. NMR experiments and X-ray analyses allowed for the observation of the formation of zwitterionic active species as well as their degradation pathway.
authors.affiliation: IFP Energies nouvelles, Rond-point de l'échangeur de Solaize, BP 3, 69360, Solaize, France.
authors.forename: Rudy
authors.initials: R
authors.lastname: Lhermet
authors.affiliation: IFP Energies nouvelles, Rond-point de l'échangeur de Solaize, BP 3, 69360, Solaize, France.
authors.forename: Emile
authors.initials: E
authors.lastname: Moser
authors.affiliation: Centre de Diffractométrie Henri Longchambon, Université de Lyon, 5 rue de La Doua, 69100, Villeurbanne, France.
authors.forename: Erwann
authors.initials: E
authors.lastname: Jeanneau
authors.affiliation: IFP Energies nouvelles, Rond-point de l'échangeur de Solaize, BP 3, 69360, Solaize, France.
authors.forename: Hélène
authors.initials: H
authors.lastname: Olivier-Bourbigou
authors.affiliation: IFP Energies nouvelles, Rond-point de l'échangeur de Solaize, BP 3, 69360, Solaize, France.
authors.forename: Pierre-Alain R
authors.identifier: http://orcid.org/0000-0001-6788-8663
authors.initials: PR
authors.lastname: Breuil
keywords: Lewis acid interaction; homogeneous catalysis; nickel; outer-sphere coordination; secondary phosphine oxide ligand