Outer‐Sphere Reactivity Shift of Secondary Phosphine Oxide‐Based Nickel Complexes: From Ethylene Hydrophosphinylation to Oligomerization
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 migrator...
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| Published in | Chemistry : a European journal Vol. 23; no. 31; pp. 7433 - 7437 |
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| Main Authors | , , , , |
| Format | Journal Article |
| Language | English |
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01.06.2017
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| 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(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. |
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| AbstractList | A new dimension for secondary phosphineoxide (SPOs) ligands is described in this article. Demonstratedon original p-allylic nickel structures, these self-assembledcomplexes trigger catalytic hydrophosphinylationreactions. Addition of a Lewis acid B(C6F5)3 switches the reactivitytowards migratory insertion and thus ethylene oligomerizationthrough an unprecedented outer-sphere interactionwith the coordinated SPO ligand. NMR experimentsand X-ray analyses allowed for the observation ofthe formation of zwitterionic active species as well as theirdegradation pathway. 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. 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 F ) 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. 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. 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(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. 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. |
| Author | Moser, Emile Olivier‐Bourbigou, Hélène Lhermet, Rudy Jeanneau, Erwann Breuil, Pierre‐Alain R. |
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| Keywords | 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 |
| Language | English |
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| Snippet | A new dimension for secondary phosphine oxide (SPOs) ligands is described in this article. Demonstrated on original π‐allylic nickel structures, these... A new dimension for secondary phosphine oxide (SPOs) ligands is described in this article. Demonstrated on original π-allylic nickel structures, these... Abstract A new dimension for secondary phosphine oxide (SPOs) ligands is described in this article. Demonstrated on original π‐allylic nickel structures, these... A new dimension for secondary phosphineoxide (SPOs) ligands is described in this article. Demonstratedon original p-allylic nickel structures, these... |
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| SubjectTerms | 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 |
| Title | Outer‐Sphere Reactivity Shift of Secondary Phosphine Oxide‐Based Nickel Complexes: From Ethylene Hydrophosphinylation to Oligomerization |
| URI | https://onlinelibrary.wiley.com/doi/abs/10.1002%2Fchem.201701414 https://www.ncbi.nlm.nih.gov/pubmed/28393410 https://www.proquest.com/docview/1904145723 https://search.proquest.com/docview/1886356397 https://ifp.hal.science/hal-01581820 |
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