Unexpected nickel complex speciation unlocks alternative pathways for the reactions of alkyl halides with dppf-nickel(0)

Megan E. Greaves; Thomas O. Ronson; Guy C. Lloyd-Jones; Feliu Maseras; Stephen Sproules; David J. Nelson

doi:10.1021/acscatal.0c02514

Unexpected nickel complex speciation unlocks alternative pathways for the reactions of alkyl halides with dppf-nickel(0)

Megan E. Greaves, Thomas O. Ronson, Guy C. Lloyd-Jones, Feliu Maseras, Stephen Sproules, David J. Nelson

Pure And Applied Chemistry

Research output: Contribution to journal › Article › peer-review

21 Citations (Scopus)

26 Downloads (Pure)

Abstract

The mechanism of the reactions between dppf-Ni0 complexes and alkyl halides has been investigated using kinetic and mechanistic experiments and DFT calculations. The active species is [Ni(κ2-dppf)(κ1-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.

Original language	English
Pages (from-to)	10717-10725
Number of pages	9
Journal	ACS Catalysis
Volume	10
Issue number	18
Early online date	21 Aug 2020
DOIs	https://doi.org/10.1021/acscatal.0c02514
Publication status	Published - 18 Sept 2020

Keywords

nickel
homogenous catalysis
cross coupling
reaction mechanisms
organometallic chemistry

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10.1021/acscatal.0c02514Licence: CC BY 4.0

Greaves-etal-2020-ACS-Catalysis-Unexpected-nickel-complex-speciation-unlocks-alternative-pathwaysFinal published version, 2.12 MBLicence: CC BY 4.0

David Nelson, MChem PhD PGDip FRSC FHEA
- david.nelsonstrath.acuk
- Pure And Applied Chemistry - Reader
Person: Academic

2 Finished

AstraZeneca ICASE
Nelson, D. (Principal Investigator)
Astra Zeneca
1/10/17 → 30/09/21
Project: Research - Studentship
Industrial CASE Account - University of Strathclyde 2017 | Greaves, Megan
Nelson, D. (Principal Investigator), Murphy, J. (Co-investigator) & Greaves, M. (Research Co-investigator)
EPSRC (Engineering and Physical Sciences Research Council)
1/10/17 → 14/09/21
Project: Research Studentship Case - Internally allocated

Data for: "Unexpected Nickel Complex Speciation Unlocks Alternative Pathways for the Reactions of Alkyl Halides with dppf-Nickel(0)"
Nelson, D. (Creator) & Greaves, M. (Creator), University of Strathclyde, 27 Aug 2020
DOI: 10.15129/7ec1bd50-bdaf-4225-b300-10f875f1f4ae
Dataset

21 Citations
1 Article

The effect of added ligands on the reactions of [Ni(COD)(dppf)] with alkyl halides: halide abstraction may be reversible
Greaves, M. E., Ronson, T. O., Maseras, F. & Nelson, D. J., 16 Jun 2021, In: Organometallics. 40, 12, p. 1997-2007 11 p.
Research output: Contribution to journal › Article › peer-review

Open Access
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10 Citations (Scopus)

46 Downloads (Pure)

1 Oral presentation

Reaction Mechanisms and Structure/ Reactivity Relationships in Nickel-Catalysed Cross-Coupling Reactions
Nelson, D. (Speaker)
26 Jun 2019
Activity: Talk or presentation types › Oral presentation

Cite this

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title = "Unexpected nickel complex speciation unlocks alternative pathways for the reactions of alkyl halides with dppf-nickel(0)",

abstract = "The mechanism of the reactions between dppf-Ni0 complexes and alkyl halides has been investigated using kinetic and mechanistic experiments and DFT calculations. The active species is [Ni(κ2-dppf)(κ1-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.",

keywords = "nickel, homogenous catalysis, cross coupling, reaction mechanisms, organometallic chemistry",

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AU - Greaves, Megan E.

AU - Ronson, Thomas O.

AU - Lloyd-Jones, Guy C.

AU - Maseras, Feliu

AU - Sproules, Stephen

AU - Nelson, David J.

PY - 2020/9/18

Y1 - 2020/9/18

N2 - The mechanism of the reactions between dppf-Ni0 complexes and alkyl halides has been investigated using kinetic and mechanistic experiments and DFT calculations. The active species is [Ni(κ2-dppf)(κ1-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.

AB - The mechanism of the reactions between dppf-Ni0 complexes and alkyl halides has been investigated using kinetic and mechanistic experiments and DFT calculations. The active species is [Ni(κ2-dppf)(κ1-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.

KW - nickel

KW - homogenous catalysis

KW - cross coupling

KW - reaction mechanisms

KW - organometallic chemistry

U2 - 10.1021/acscatal.0c02514

DO - 10.1021/acscatal.0c02514

M3 - Article

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VL - 10

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EP - 10725

JO - ACS Catalysis

JF - ACS Catalysis

IS - 18

ER -

Unexpected nickel complex speciation unlocks alternative pathways for the reactions of alkyl halides with dppf-nickel(0)

Abstract

Keywords

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Profiles

David Nelson, MChem PhD PGDip FRSC FHEA

Projects

AstraZeneca ICASE

Industrial CASE Account - University of Strathclyde 2017 | Greaves, Megan

Datasets

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

Research output

The effect of added ligands on the reactions of [Ni(COD)(dppf)] with alkyl halides: halide abstraction may be reversible

Activities

Reaction Mechanisms and Structure/ Reactivity Relationships in Nickel-Catalysed Cross-Coupling Reactions

Cite this