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

• Published in: Chemistry : a European journal Vol. 23; no. 31; pp. 7433 - 7437
• Main Authors: Lhermet, Rudy, Moser, Emile, Jeanneau, Erwann, Olivier‐Bourbigou, Hélène, Breuil, Pierre‐Alain R.
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01.06.2017; Wiley-VCH Verlag
• Subjects: Catalysis; Chemical Sciences; Chemistry; Ethylene; homogeneous catalysis; Lewis acid; Lewis acid interaction; Ligands; Nickel; NMR; Nuclear magnetic resonance; Oligomerization; outer-sphere coordination; Phosphine oxide; secondary phosphine oxide ligand; Self-assembly; Switches; nickel; homogeneous catalysis; secondary phosphine oxide ligand; Lewis acid interaction; outer-sphere coordination; Cayalysts; Stable palladium catalysis; Olefins; Homogeneous catalysis; Platinium; Nickel; Secondary phosphine oxide ligand; Dimerization; Outer-pherecoordination; Hydrogeznation
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201701414

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)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. On the outer sphere: 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)3 switches the reactivity towards migratory insertion and thus ethylene oligomerization through an unprecedented outer‐sphere interaction with the coordinated SPO ligand.