Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0)

[Image: see text] The mechanism of the reactions between dppf-Ni(0) complexes and alkyl halides has been investigated using kinetic and mechanistic experiments and DFT calculations. The active species is [Ni(κ(2)-dppf)(κ(1)-dppf)], which undergoes a halide abstraction reaction with alkyl halides and...

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Autores principales: Greaves, Megan E., Ronson, Thomas O., Lloyd-Jones, Guy C., Maseras, Feliu, Sproules, Stephen, Nelson, David J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2020
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7507766/
https://www.ncbi.nlm.nih.gov/pubmed/32983589
http://dx.doi.org/10.1021/acscatal.0c02514
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author Greaves, Megan E.
Ronson, Thomas O.
Lloyd-Jones, Guy C.
Maseras, Feliu
Sproules, Stephen
Nelson, David J.
author_facet Greaves, Megan E.
Ronson, Thomas O.
Lloyd-Jones, Guy C.
Maseras, Feliu
Sproules, Stephen
Nelson, David J.
author_sort Greaves, Megan E.
collection PubMed
description [Image: see text] The mechanism of the reactions between dppf-Ni(0) complexes and alkyl halides has been investigated using kinetic and mechanistic experiments and DFT calculations. The active species is [Ni(κ(2)-dppf)(κ(1)-dppf)], which undergoes a halide abstraction reaction with alkyl halides and rapidly captures the alkyl radical that is formed. The rates of the reactions of [Ni(COD)(dppf)] with alkyl halides and the yields of prototypical nickel-catalyzed Kumada cross-coupling reactions of alkyl halides are shown to be significantly improved by the addition of free dppf ligand.
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spelling pubmed-75077662020-09-23 Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0) Greaves, Megan E. Ronson, Thomas O. Lloyd-Jones, Guy C. Maseras, Feliu Sproules, Stephen Nelson, David J. ACS Catal [Image: see text] The mechanism of the reactions between dppf-Ni(0) complexes and alkyl halides has been investigated using kinetic and mechanistic experiments and DFT calculations. The active species is [Ni(κ(2)-dppf)(κ(1)-dppf)], which undergoes a halide abstraction reaction with alkyl halides and rapidly captures the alkyl radical that is formed. The rates of the reactions of [Ni(COD)(dppf)] with alkyl halides and the yields of prototypical nickel-catalyzed Kumada cross-coupling reactions of alkyl halides are shown to be significantly improved by the addition of free dppf ligand. American Chemical Society 2020-08-21 2020-09-18 /pmc/articles/PMC7507766/ /pubmed/32983589 http://dx.doi.org/10.1021/acscatal.0c02514 Text en Copyright © 2020 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
spellingShingle Greaves, Megan E.
Ronson, Thomas O.
Lloyd-Jones, Guy C.
Maseras, Feliu
Sproules, Stephen
Nelson, David J.
Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0)
title Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0)
title_full Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0)
title_fullStr Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0)
title_full_unstemmed Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0)
title_short Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0)
title_sort unexpected nickel complex speciation unlocks alternative pathways for the reactions of alkyl halides with dppf-nickel(0)
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7507766/
https://www.ncbi.nlm.nih.gov/pubmed/32983589
http://dx.doi.org/10.1021/acscatal.0c02514
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