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

Bajo, Sonia and Laidlaw, Gillian and Kennedy, Alan R. and Sproules, Stephen and Nelson, David J. (2017) Oxidative addition of aryl electrophiles to a prototypical nickel(0) complex : mechanism and structure/reactivity relationships. Organometallics, 36 (8). pp. 1662-1672. ISSN 0276-7333 (https://doi.org/10.1021/acs.organomet.7b00208)

[thumbnail of Bajo-etal-Organometallics-2017-Oxidative-addition-of-aryl-electrophiles]
Preview
 Text. Filename: Bajo_etal_Organometallics_2017_Oxidative_addition_of_aryl_electrophiles.pdf
Final Published Version
License: Creative Commons Attribution 4.0 logo
Download (2MB)| Preview

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.

ORCID iDs

Bajo, Sonia ORCID logoORCID: https://orcid.org/0000-0003-4803-566X, Laidlaw, Gillian, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Sproules, Stephen and Nelson, David J. ORCID logoORCID: https://orcid.org/0000-0002-9461-5182;
  • Item type:Article
    ID code:60367
    Dates:
    Date
    Event
    24 April 2017
    Published
    6 April 2017
    Published Online
    29 March 2017
    Accepted
    Notes: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.
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:30 Mar 2017 09:30
    Last modified:11 Nov 2024 11:40
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/60367
CORE (COnnecting REpositories)