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

Leonie J. Bole, Marina Uzelac, Alberto Hernán-Gómez, Alan R. Kennedy, Charles T. O'Hara, Eva Hevia

Research output: Contribution to journalArticlepeer-review

10 Citations (SciVal)


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.

Original languageEnglish
Pages (from-to)13784-13796
Number of pages13
JournalInorganic Chemistry
Issue number18
Early online date30 Jun 2021
Publication statusPublished - 20 Sept 2021

Bibliographical note

Funding Information:
We thank the University of Bern and the SNF (Grant 188573) for the generous sponsorship of this research. The X-ray crystal structure determination service unit of the Department of Chemistry and Biochemistry of the University of Bern is acknowledged for measuring, solving, refining, and summarizing the structures of compounds 3 and 4 . The Synergy diffractometer was partially funded by the SNF within the R’Equip programme (Project 206021_177033). A.H.-G. acknowledges the Comunidad de Madrid and Universidad de Alcalá for the funding through the Research Talent Attraction Program (2018-T1/AMB-11478) and Programa Estímulo a la Investigación de Jovenes Investigadores (CM/JIN/2019-030).

Publisher Copyright:

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


Dive into the research topics of 'Progressing the frustrated Lewis pair abilities of N-Heterocyclic carbene/GaR3 combinations for catalytic hydroboration of aldehydes and ketones'. Together they form a unique fingerprint.

Cite this