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Start Over Author "Pierre-Alain Breuil" Journal chemistry (weinheim an der bergstrasse, germany)
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1. Outer-Sphere Reactivity Shift of Secondary Phosphine Oxide-Based Nickel Complexes: From Ethylene Hydrophosphinylation to Oligomerization

Author

Rudy Lhermet, Helene Olivier-Bourbigou, Emile Moser, Erwann Jeanneau, and Pierre-Alain Breuil

Subjects
Phosphine oxide, Ethylene, 010405 organic chemistry, Ligand, Organic Chemistry, Migratory insertion, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Polymer chemistry, Outer sphere electron transfer, Reactivity (chemistry), Lewis acids and bases
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.

Published
2017

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