Nickel versus palladium in cross-coupling catalysis

on the role of substrate coordination to zerovalent metal complexes

Research output: Contribution to journalArticle

Abstract

We report a detailed comparison of the effect of coordinating functional groups on the performance of Suzuki-Miyaura reactions catalysed by nickel and palladium, using competition experiments, robustness screening, and density functional theory calculations. Nickel can interact with a variety of functional groups, which manifests as selectivity in competitive cross-coupling reactions. The presence of these functional groups on exogenous additives has a range of effects on cross-coupling reactions that range from a slight improvement in yield to the complete cessation of the reaction. In contrast, palladium does not interact sufficiently strongly with these functional groups to induce selectivity in cross-coupling reactions; the selectivity of palladium-catalysed cross-coupling reactions is predominantly governed by aryl halide electronic properties.
Original languageEnglish
Number of pages8
JournalSynthesis
Publication statusAccepted/In press - 16 Dec 2019

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Coordination Complexes
Palladium
Metal complexes
Nickel
Functional groups
Catalysis
Substrates
Electronic properties
Density functional theory
Screening
Experiments

Keywords

  • nickel catalysis
  • cross-coupling
  • robustness screening
  • reaction mechanisms
  • structure/activity relationships

Cite this

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title = "Nickel versus palladium in cross-coupling catalysis: on the role of substrate coordination to zerovalent metal complexes",
abstract = "We report a detailed comparison of the effect of coordinating functional groups on the performance of Suzuki-Miyaura reactions catalysed by nickel and palladium, using competition experiments, robustness screening, and density functional theory calculations. Nickel can interact with a variety of functional groups, which manifests as selectivity in competitive cross-coupling reactions. The presence of these functional groups on exogenous additives has a range of effects on cross-coupling reactions that range from a slight improvement in yield to the complete cessation of the reaction. In contrast, palladium does not interact sufficiently strongly with these functional groups to induce selectivity in cross-coupling reactions; the selectivity of palladium-catalysed cross-coupling reactions is predominantly governed by aryl halide electronic properties.",
keywords = "nickel catalysis, cross-coupling, robustness screening, reaction mechanisms, structure/activity relationships",
author = "Cooper, {Alasdair K.} and Burton, {Paul M.} and Nelson, {David J.}",
year = "2019",
month = "12",
day = "16",
language = "English",
journal = "Synthesis",
issn = "0039-7881",
publisher = "Georg Thieme Verlag",

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T1 - Nickel versus palladium in cross-coupling catalysis

T2 - on the role of substrate coordination to zerovalent metal complexes

AU - Cooper, Alasdair K.

AU - Burton, Paul M.

AU - Nelson, David J.

PY - 2019/12/16

Y1 - 2019/12/16

N2 - We report a detailed comparison of the effect of coordinating functional groups on the performance of Suzuki-Miyaura reactions catalysed by nickel and palladium, using competition experiments, robustness screening, and density functional theory calculations. Nickel can interact with a variety of functional groups, which manifests as selectivity in competitive cross-coupling reactions. The presence of these functional groups on exogenous additives has a range of effects on cross-coupling reactions that range from a slight improvement in yield to the complete cessation of the reaction. In contrast, palladium does not interact sufficiently strongly with these functional groups to induce selectivity in cross-coupling reactions; the selectivity of palladium-catalysed cross-coupling reactions is predominantly governed by aryl halide electronic properties.

AB - We report a detailed comparison of the effect of coordinating functional groups on the performance of Suzuki-Miyaura reactions catalysed by nickel and palladium, using competition experiments, robustness screening, and density functional theory calculations. Nickel can interact with a variety of functional groups, which manifests as selectivity in competitive cross-coupling reactions. The presence of these functional groups on exogenous additives has a range of effects on cross-coupling reactions that range from a slight improvement in yield to the complete cessation of the reaction. In contrast, palladium does not interact sufficiently strongly with these functional groups to induce selectivity in cross-coupling reactions; the selectivity of palladium-catalysed cross-coupling reactions is predominantly governed by aryl halide electronic properties.

KW - nickel catalysis

KW - cross-coupling

KW - robustness screening

KW - reaction mechanisms

KW - structure/activity relationships

UR - https://www.thieme-connect.com/products/ejournals/journal/10.1055/s-00000084

M3 - Article

JO - Synthesis

JF - Synthesis

SN - 0039-7881

ER -