Outer-Sphere Reactivity Shift of Secondary Phosphine Oxide-Based Nickel Complexes: From Ethylene Hydrophosphinylation to Oligomerization - Archive ouverte HAL Access content directly
Journal Articles Chemistry - A European Journal Year : 2017

Outer-Sphere Reactivity Shift of Secondary Phosphine Oxide-Based Nickel Complexes: From Ethylene Hydrophosphinylation to Oligomerization

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Abstract

A new dimension for secondary phosphine oxide (SPOs) ligands is described in this article. Demonstrated on original p-allylic nickel structures, these self-assembled complexes trigger catalytic hydrophosphinylation reactions. Addition of a Lewis acid B(C6F5)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.
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hal-01581820 , version 1 (05-09-2017)

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Rudy Lhermet, Emile Moser, Erwann Jeanneau, Hélène Olivier-Bourbigou, Pierre-Alain R. Breuil. Outer-Sphere Reactivity Shift of Secondary Phosphine Oxide-Based Nickel Complexes: From Ethylene Hydrophosphinylation to Oligomerization. Chemistry - A European Journal, 2017, 23 (31), pp.7433 - 7437. ⟨10.1002/chem.201701414⟩. ⟨hal-01581820⟩

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