Magnesium-catalysed nitrile hydroboration

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Weetman, Catherine and Anker, Mathew D. and Arrowsmith, Merle and Hill, Michael S. and Kociok-Köhn, Gabriele and Liptrot, David J. and Mahon, Mary F. (2016) Magnesium-catalysed nitrile hydroboration. Chemical Science, 2016 (1). pp. 628-641. ISSN 2041-6539 (https://doi.org/10.1039/C5SC03114A)

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Abstract

A β-diketiminato n-butylmagnesium complex is presented as a selective precatalyst for the reductive hydroboration of organic nitriles with pinacolborane (HBpin). Stoichiometric reactivity studies indicate that catalytic turnover ensues through the generation of magnesium aldimido, aldimidoborate and borylamido intermediates, which are formed in a sequence of intramolecular nitrile insertion and inter- and intramolecular B–H metathesis events. Kinetic studies highlight variations in mechanism for the catalytic dihydroboration of alkyl nitriles, aryl nitriles bearing electron withdrawing (Ar(EWG)CN) and aryl nitriles bearing electron donating (Ar(EDG)CN) substitution patterns. Kinetic isotope effects (KIEs) for catalysis performed with DBpin indicate that B–H bond breaking and C–H bond forming reactions are involved in the rate determining processes during the dihydroboration of alkyl nitriles and Ar(EDG)CN substrates, which display divergent first and second order rate dependences on [HBpin] respectively. In contrast, the hydroboration of Ar(EWG)CN substrates provides no KIE and HBpin is not implicated in the rate determining process during catalysis. Irrespective of these differences, a common mechanism is proposed in which the rate determining steps are deduced to vary through the establishment of several pre-equilibria, the relative positions of which are determined by the respective stabilities of the dimeric and monomeric magnesium aldimide and magnesium aldimidoborate intermediates as a result of adjustments to the basicity of the nitrile substrate. More generally, these observations indicate that homogeneous processes performed under heavier alkaline earth catalysis are likely to demonstrate previously unappreciated mechanistic diversity.

ORCID iDs

Weetman, Catherine ORCID logoORCID: https://orcid.org/0000-0001-5643-9256, Anker, Mathew D., Arrowsmith, Merle, Hill, Michael S., Kociok-Köhn, Gabriele, Liptrot, David J. and Mahon, Mary F.;
  • Item type:Article
    ID code:73658
    Dates:
    Date
    Event
    1 January 2016
    Published
    20 October 2015
    Published Online
    19 October 2015
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:20 Aug 2020 09:44
    Last modified:27 Nov 2024 08:37
    URI:https://strathprints.strath.ac.uk/id/eprint/73658
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