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Nickel boryl complexes and the nickel-catalyzed alkyne borylation

Tendera, Lukas, Fantuzzi, Felipe, Marder, Todd B., Radius, Udo (2023) Nickel boryl complexes and the nickel-catalyzed alkyne borylation. Chemical Science, 14 (8). pp. 2215-2228. ISSN 2041-6520. E-ISSN 2041-6539. (doi:10.1039/D2SC04690C) (KAR id:99827)

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The first nickel bis-boryl complexes cis [Ni(iPr2ImMe)2(Bcat)2], cis [Ni(iPr2ImMe)2(Bpin)2] and cis [Ni(iPr2ImMe)2(Beg)2] are reported, which were prepared via the reaction of a source of [Ni(iPr2ImMe)2] with the diboron(4) compounds B2cat2, B2pin2 and B2eg2 (iPr2ImMe = 1,3-di-iso-propyl-4,5-dimethylimidazolin-2-ylidene; B2cat2 = bis(catecholato)diboron; B2pin2 = bis(pinacolato)diboron; B2eg2 = bis(ethylene glycolato)diboron). X-ray diffraction and DFT calculations strongly suggest that a delocalized, multicenter bonding scheme dictates the bonding situation of the NiB2 moiety in these square planar complexes, reminiscent to the bonding situation of “non-classical” H2 complexes. [Ni(iPr2ImMe)2] also efficiently catalyzes the diboration of alkynes using B2cat2 as the boron source under mild conditions. In contrast to the known platinum-catalyzed diboration, the nickel system follows a different mechanistic pathway, which not only provides the 1,2 borylation product in excellent yields, but also provides, additionally, an efficient approach to other products such as C–C coupled borylation products or rare tetra-borylated compounds. The mechanism of the nickel-catalyzed alkyne borylation was examined by means of stoichiometric reactions and DFT calculations. Oxidative addition of the diboron reagent to nickel is not dominant; the first steps of the catalytic cycle are coordination of the alkyne to [Ni(iPr2ImMe)2] and subsequent borylation at the coordinated and, thus, activated alkyne to yield complexes of the type [Ni(NHC)2(η2-cis-(Bcat)(R)C=C(R)(Bcat))], exemplified by the isolation and structural characterization of [Ni(iPr2ImMe)2(η2-cis-(Bcat)(Me)C=C(Me)(Bcat))] and [Ni(iPr2ImMe)2(η2-cis-(Bcat)(H7C3)C=C(C3H7)(Bcat))].

Item Type: Article
DOI/Identification number: 10.1039/D2SC04690C
Uncontrolled keywords: General Chemistry
Subjects: Q Science > QD Chemistry
Divisions: Divisions > Division of Natural Sciences > Chemistry and Forensics
Funders: University of Würzburg (
University of Kent (
Depositing User: Felipe Fantuzzi
Date Deposited: 31 Jan 2023 18:01 UTC
Last Modified: 15 Mar 2023 15:58 UTC
Resource URI: (The current URI for this page, for reference purposes)
Fantuzzi, Felipe:
Marder, Todd B.:
Radius, Udo:
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