Oxidative addition of aryl electrophiles to a prototypical nickel(0) complex: mechanism and structure/reactivity relationships

Sonia Bajo, Gillian Laidlaw, Alan R. Kennedy, Stephen Sproules, David J. Nelson

Research output: Contribution to journalArticle

41 Citations (Scopus)

Abstract

Detailed kinetic studies of the reaction of a model Ni0 complex with a range of aryl electrophiles have been conducted. The reactions proceed via a fast ligand exchange pre-equilibrium, followed by oxidative addition to produce either [NiIX(dppf)] (and biaryl) or [NiII(Ar)X(dppf)]; the ortho substituent of the aryl halide determines selectivity between these possibilities. A reactivity scale is presented in which a range of substrates is quantitatively ranked in order of the rate at which they undergo oxidative addition. The rate of oxidative addition is loosely correlated to conversion in prototypical cross-coupling reactions. Substrates that lead to NiI products in kinetic experiments produce more homocoupling products under catalytic conditions.
LanguageEnglish
Pages1662-1672
Number of pages33
JournalOrganometallics
Volume36
Issue number8
Early online date6 Apr 2017
DOIs
Publication statusE-pub ahead of print - 6 Apr 2017

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Nickel
reactivity
nickel
Kinetics
Substrates
Ligands
cross coupling
kinetics
products
halides
selectivity
ligands
Experiments

Keywords

  • nickel
  • oxidative addition
  • mechanistic studies
  • kinetics
  • cross coupling

Cite this

@article{d416d7f98fc84494b3384e0b93946beb,
title = "Oxidative addition of aryl electrophiles to a prototypical nickel(0) complex: mechanism and structure/reactivity relationships",
abstract = "Detailed kinetic studies of the reaction of a model Ni0 complex with a range of aryl electrophiles have been conducted. The reactions proceed via a fast ligand exchange pre-equilibrium, followed by oxidative addition to produce either [NiIX(dppf)] (and biaryl) or [NiII(Ar)X(dppf)]; the ortho substituent of the aryl halide determines selectivity between these possibilities. A reactivity scale is presented in which a range of substrates is quantitatively ranked in order of the rate at which they undergo oxidative addition. The rate of oxidative addition is loosely correlated to conversion in prototypical cross-coupling reactions. Substrates that lead to NiI products in kinetic experiments produce more homocoupling products under catalytic conditions.",
keywords = "nickel, oxidative addition, mechanistic studies, kinetics, cross coupling",
author = "Sonia Bajo and Gillian Laidlaw and Kennedy, {Alan R.} and Stephen Sproules and Nelson, {David J.}",
note = "Copyright {\circledC} 2017 American Chemical Society. Bajo, S., Laidlaw, G., Kennedy, A. R., Sproules, S., & Nelson, D. J. (2017). Oxidative addition of aryl electrophiles to a prototypical nickel(0) complex: mechanism and structure/reactivity relationships. Organometallics, 1-33. Article accepted for publication by ACS.",
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Oxidative addition of aryl electrophiles to a prototypical nickel(0) complex : mechanism and structure/reactivity relationships. / Bajo, Sonia; Laidlaw, Gillian; Kennedy, Alan R.; Sproules, Stephen; Nelson, David J.

In: Organometallics, Vol. 36, No. 8, 06.04.2017, p. 1662-1672.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Oxidative addition of aryl electrophiles to a prototypical nickel(0) complex

T2 - Organometallics

AU - Bajo, Sonia

AU - Laidlaw, Gillian

AU - Kennedy, Alan R.

AU - Sproules, Stephen

AU - Nelson, David J.

N1 - Copyright © 2017 American Chemical Society. Bajo, S., Laidlaw, G., Kennedy, A. R., Sproules, S., & Nelson, D. J. (2017). Oxidative addition of aryl electrophiles to a prototypical nickel(0) complex: mechanism and structure/reactivity relationships. Organometallics, 1-33. Article accepted for publication by ACS.

PY - 2017/4/6

Y1 - 2017/4/6

N2 - Detailed kinetic studies of the reaction of a model Ni0 complex with a range of aryl electrophiles have been conducted. The reactions proceed via a fast ligand exchange pre-equilibrium, followed by oxidative addition to produce either [NiIX(dppf)] (and biaryl) or [NiII(Ar)X(dppf)]; the ortho substituent of the aryl halide determines selectivity between these possibilities. A reactivity scale is presented in which a range of substrates is quantitatively ranked in order of the rate at which they undergo oxidative addition. The rate of oxidative addition is loosely correlated to conversion in prototypical cross-coupling reactions. Substrates that lead to NiI products in kinetic experiments produce more homocoupling products under catalytic conditions.

AB - Detailed kinetic studies of the reaction of a model Ni0 complex with a range of aryl electrophiles have been conducted. The reactions proceed via a fast ligand exchange pre-equilibrium, followed by oxidative addition to produce either [NiIX(dppf)] (and biaryl) or [NiII(Ar)X(dppf)]; the ortho substituent of the aryl halide determines selectivity between these possibilities. A reactivity scale is presented in which a range of substrates is quantitatively ranked in order of the rate at which they undergo oxidative addition. The rate of oxidative addition is loosely correlated to conversion in prototypical cross-coupling reactions. Substrates that lead to NiI products in kinetic experiments produce more homocoupling products under catalytic conditions.

KW - nickel

KW - oxidative addition

KW - mechanistic studies

KW - kinetics

KW - cross coupling

UR - http://pubs.acs.org/journal/orgnd7

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