On the reactions of (hetero)aryl and vinyl triflates with [Ni(COD)(dppf)]

Nicholas C.C. McVeigh; Megan E. Greaves; Rachel H. Munday; Thomas O. Ronson; Scott Rice; Stephen Sproules; David J. Nelson

doi:10.1039/D6CY00261G

On the reactions of (hetero)aryl and vinyl triflates with [Ni(COD)(dppf)]

Nicholas C.C. McVeigh, Megan E. Greaves, Rachel H. Munday, Thomas O. Ronson, Scott Rice, Stephen Sproules, David J. Nelson

Pure And Applied Chemistry

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Abstract

We report the experimental and computational investigations of the reactions of aryl, heteroaryl, and vinyl triflates with a model nickel(0) complex. While the reactions of most (hetero)aryl and vinyl triflates behave straightforwardly, the reactions of 3-pyridinyl triflates are rather different; under reaction conditions where the organotriflates are used in vast excess there is not a simple pseudo-first order behaviour. These reactions are further explored using DFT calculations, which show that both three- and five-centred oxidative addition transition states are viable, but that the experimentally-observed order of reactivity is not readily reproduced by considering a simple oxidative addition pathway.

Original language	English
Journal	Catalysis Science and Technology
Early online date	19 May 2026
DOIs	https://doi.org/10.1039/D6CY00261G
Publication status	E-pub ahead of print - 19 May 2026

Funding

NCCM, MEG, and DJN thank AstraZeneca and the UK Research and Innovation Engineering and Physical Sciences Research Council (UKRI EPSRC) for studentship funding (EP/W524670/1 and EP/R512114/1).

Keywords

nickel
catalysis
reaction mechanisms

Access to Document

10.1039/D6CY00261GLicence: CC BY 3.0

McVeigh-etal-CST-2026-On-the-reactions-of-heteroaryl-and-vinyl-triflatesFinal published version, 2.45 MBLicence: CC BY 3.0

Cite this

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title = "On the reactions of (hetero)aryl and vinyl triflates with [Ni(COD)(dppf)]",

abstract = "We report the experimental and computational investigations of the reactions of aryl, heteroaryl, and vinyl triflates with a model nickel(0) complex. While the reactions of most (hetero)aryl and vinyl triflates behave straightforwardly, the reactions of 3-pyridinyl triflates are rather different; under reaction conditions where the organotriflates are used in vast excess there is not a simple pseudo-first order behaviour. These reactions are further explored using DFT calculations, which show that both three- and five-centred oxidative addition transition states are viable, but that the experimentally-observed order of reactivity is not readily reproduced by considering a simple oxidative addition pathway. ",

keywords = "nickel, catalysis, reaction mechanisms",

author = "McVeigh, \{Nicholas C.C.\} and Greaves, \{Megan E.\} and Munday, \{Rachel H.\} and Ronson, \{Thomas O.\} and Scott Rice and Stephen Sproules and Nelson, \{David J.\}",

year = "2026",

month = may,

day = "19",

doi = "10.1039/D6CY00261G",

language = "English",

journal = "Catalysis Science and Technology",

issn = "2044-4753",

publisher = "Royal Society of Chemistry",

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T1 - On the reactions of (hetero)aryl and vinyl triflates with [Ni(COD)(dppf)]

AU - McVeigh, Nicholas C.C.

AU - Greaves, Megan E.

AU - Munday, Rachel H.

AU - Ronson, Thomas O.

AU - Rice, Scott

AU - Sproules, Stephen

AU - Nelson, David J.

PY - 2026/5/19

Y1 - 2026/5/19

N2 - We report the experimental and computational investigations of the reactions of aryl, heteroaryl, and vinyl triflates with a model nickel(0) complex. While the reactions of most (hetero)aryl and vinyl triflates behave straightforwardly, the reactions of 3-pyridinyl triflates are rather different; under reaction conditions where the organotriflates are used in vast excess there is not a simple pseudo-first order behaviour. These reactions are further explored using DFT calculations, which show that both three- and five-centred oxidative addition transition states are viable, but that the experimentally-observed order of reactivity is not readily reproduced by considering a simple oxidative addition pathway.

AB - We report the experimental and computational investigations of the reactions of aryl, heteroaryl, and vinyl triflates with a model nickel(0) complex. While the reactions of most (hetero)aryl and vinyl triflates behave straightforwardly, the reactions of 3-pyridinyl triflates are rather different; under reaction conditions where the organotriflates are used in vast excess there is not a simple pseudo-first order behaviour. These reactions are further explored using DFT calculations, which show that both three- and five-centred oxidative addition transition states are viable, but that the experimentally-observed order of reactivity is not readily reproduced by considering a simple oxidative addition pathway.

KW - nickel

KW - catalysis

KW - reaction mechanisms

UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15000565/v1

U2 - 10.1039/D6CY00261G

DO - 10.1039/D6CY00261G

M3 - Article

SN - 2044-4753

JO - Catalysis Science and Technology

JF - Catalysis Science and Technology

ER -

On the reactions of (hetero)aryl and vinyl triflates with [Ni(COD)(dppf)]

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

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

Data for: "On the reactions of (hetero)aryl and vinyl triflates with [Ni(COD)(dppf)]"

ARCHIE-WeSt (UOSHPC)

AVI400 NMR Spectrometer

AVII+600 NMR Spectrometer

Understanding reactions between Nickel(0) and substrates relevant to cross-coupling reactions

Cite this

On the reactions of (hetero)aryl and vinyl triflates with [Ni(COD)(dppf)]

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Projects

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

Datasets

Data for: "On the reactions of (hetero)aryl and vinyl triflates with [Ni(COD)(dppf)]"

Equipment

ARCHIE-WeSt (UOSHPC)

AVI400 NMR Spectrometer

AVII+600 NMR Spectrometer

Student theses

Understanding reactions between Nickel(0) and substrates relevant to cross-coupling reactions

Cite this