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Outer-Sphere Reactivity Shift of Secondary Phosphine Oxide-Based Nickel Complexes: From Ethylene Hydrophosphinylation
Rudy Lhermet1, Emile Moser1, Erwann Jeanneau2
1IFP Energies nouvelles, Rond-point de l'échangeur de Solaize, BP 3, 69360, Solaize, France.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|April 11, 2017
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(C6 F5 )3 switches 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.