Progressing the frustrated Lewis pair abilities of N‐heterocyclic carbene/GaR3 combinations for catalytic hydroboration of aldehydes and ketones

Bole, Leonie J. and Uzelac, Marina and Hernán-Gómez, Alberto and Kennedy, Alan R. and O'Hara, Charles T. and Hevia, Eva (2021) Progressing the frustrated Lewis pair abilities of N‐heterocyclic carbene/GaR3 combinations for catalytic hydroboration of aldehydes and ketones. Inorganic Chemistry, 60 (18). pp. 13784-13796. ISSN 1520-510X (https://doi.org/10.1021/acs.inorgchem.1c01276)

[thumbnail of Bole-etal-IC-2021-Progressing-the-frustrated-Lewis-pair-abilities-of-N-heterocyclic-carbene]
Preview
 Text. Filename: Bole_etal_IC_2021_Progressing_the_frustrated_Lewis_pair_abilities_of_N_heterocyclic_carbene.pdf
Accepted Author Manuscript
Download (1MB)| Preview

Abstract

Exploiting the steric incompatibility of the tris-(alkyl)gallium GaR3 (R = CH2SiMe3) and the bulky N-heterocyclic carbene (NHC) 1,3-bis(tert-butyl)imidazol-2-ylidene (ItBu), here we report the B−H bond activation of pinacolborane (HBPin), which has led to the isolation and structural authentication of a novel ion pair, [{ItBu-BPin}+{GaR3(μ-H)-GaR3}−] (2). Contrastingly, neither ItBu or GaR3 was able to react with HBPin under the conditions of this study. Combining an NHC-stabilized borenium cation, [{ItBu-BPin}+], with an anionic dinuclear gallate, [{GaR3(μ-H)GaR3}−], 2 proved to be unstable in solution at room temperature, evolving to the abnormal NHC-Ga complex [BPinC{{N(tBu)]2CHCGa(R)3}] (3). Interestingly, the structural isomer of 2, with the borenium cation residing at the C4 position of the carbene, [{aItBu-BPin}+{GaR3(μ-H)GaR3}−] (4), was obtained when the abnormal NHC complex [aItBu·GaR3] (1) was heated to 70 °C with HBPin, demonstrating that, under these forced conditions, it is possible to induce thermal frustration of the Lewis base/Lewis acid components of 1, enabling the activation of HBPin. Building on these stoichiometric studies, the frustrated Lewis pair (FLP) reactivity observed for the GaR3/ItBu combination with HBPin could then be upgraded to catalytic regimes, allowing the efficient hydroboration of a range of aldehydes and ketones under mild reaction conditions. Mechanistic insights into the possible reaction pathway involved in this process have been gained by combining kinetic investigations with a comparative study of the catalytic capabilities of several gallium and borenium species related to 2. Disclosing a new cooperative partnership, reactions are proposed to occur via the formation of a highly reactive monomeric hydride gallate, [{ItBu- BPin}+{GaR3(H)}−] (I). Each anionic and cationic component of I plays a key role for success of the hydroboration, with the nucleophilic monomeric gallate anion favoring the transfer of its hydride to the C=O bond of the organic substate, which in turn is activated by coordination to the borenium cation.

ORCID iDs

Bole, Leonie J., Uzelac, Marina, Hernán-Gómez, Alberto, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, O'Hara, Charles T. and Hevia, Eva;
  • Item type:Article
    ID code:77602
    Dates:
    Date
    Event
    20 September 2021
    Published
    30 June 2021
    Published Online
    7 June 2021
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:30 Aug 2021 13:30
    Last modified:17 Nov 2024 01:19
    URI:https://strathprints.strath.ac.uk/id/eprint/77602
CORE (COnnecting REpositories)