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

1 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-catalysed 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
Early online date	21 Aug 2020
DOIs	https://doi.org/10.1021/acscatal.0c02514
Publication status	E-pub ahead of print - 21 Aug 2020

Keywords

nickel
homogenous catalysis
cross coupling
reaction mechanisms
organometallic chemistry

Access to Document

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

Fingerprint Dive into the research topics of 'Unexpected nickel complex speciation unlocks alternative pathways for the reactions of alkyl halides with dppf-nickel(0)'. Together they form a unique fingerprint.

David Nelson, MChem PhD PGDip MRSC FHEA
- david.nelson@strath.ac.uk
- Pure And Applied Chemistry - Senior Lecturer
Person: Academic

2 Active

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

Cite this

@article{0d389cf0c7a74fe3926ced7e8172bc27,

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-catalysed 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",

author = "Greaves, {Megan E.} and Ronson, {Thomas O.} and Lloyd-Jones, {Guy C.} and Feliu Maseras and Stephen Sproules and Nelson, {David J.}",

year = "2020",

month = aug,

day = "21",

doi = "10.1021/acscatal.0c02514",

language = "English",

volume = "10",

pages = "10717--10725",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

}

TY - JOUR

T1 - Unexpected nickel complex speciation unlocks alternative pathways for the reactions of alkyl halides with dppf-nickel(0)

AU - Greaves, Megan E.

AU - Ronson, Thomas O.

AU - Lloyd-Jones, Guy C.

AU - Maseras, Feliu

AU - Sproules, Stephen

AU - Nelson, David J.

PY - 2020/8/21

Y1 - 2020/8/21

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-catalysed 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-catalysed 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

VL - 10

SP - 10717

EP - 10725

JO - ACS Catalysis

JF - ACS Catalysis

SN - 2155-5435

ER -

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

Abstract

Keywords

Access to Document

David Nelson, MChem PhD PGDip MRSC FHEA

AstraZeneca ICASE

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

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

Cite this