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Outer‐Sphere Reactivity Shift of Secondary Phosphine Oxide‐Based Nickel Complexes: From Ethylene Hydrophosphinylation to Oligomerization
Author(s) -
Lhermet Rudy,
Moser Emile,
Jeanneau Erwann,
OlivierBourbigou Hélène,
Breuil PierreAlain R.
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201701414
Subject(s) - reactivity (psychology) , phosphine , nickel , allylic rearrangement , ethylene , chemistry , ethylene oxide , catalysis , ligand (biochemistry) , phosphine oxide , oxide , polymer chemistry , photochemistry , stereochemistry , copolymer , organic chemistry , polymer , medicine , biochemistry , receptor , alternative medicine , pathology
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(C 6 F 5 ) 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.