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An Iridium-Stabilized Borenium Intermediate


Hamdaoui, Mustapha; Liu, Fan; Cornaton, Yann; Lu, Xingyu; Shi, Xiaohuo; Zhang, Huan; Liu, Jiyong; Spingler, Bernhard; Djukic, Jean-Pierre; Duttwyler, Simon (2022). An Iridium-Stabilized Borenium Intermediate. Journal of the American Chemical Society, 144(40):18359-18374.

Abstract

Exploration of new organometallic systems based on polyhedral boron clusters has the potential to solve challenging chemical problems such as the stabilization of reactive intermediates and transition-state-like species postulated for E–H (E = H, B, C, Si) bond activation reactions. We report on facile and clean B–H activation of a hydroborane by a new iridium boron cluster complex. The product of this reaction is an unprecedented and fully characterized transition metal-stabilized boron cation or borenium. Moreover, this intermediate bears an unusual intramolecular B···H interaction between the hydrogen originating from the activated hydroborane and the cyclometallated metal-bonded boron atom of the boron cluster. This B···H interaction is proposed to be an arrested insertion of hydrogen into the Bcage–metal bond and the initiation step for iridium “cage-walking” around the upper surface of the boron cluster. The “cage-walking” process is supported by the hydrogen–deuterium exchange observed at the boron cluster, and a mechanism is proposed on the basis of theoretical methods with a special focus on the role of noncovalent interactions. All new compounds were isolated and fully characterized by NMR spectroscopy and elemental analysis. Key compounds were studied by single crystal X-ray diffraction and X-ray photoelectron spectroscopy.

Abstract

Exploration of new organometallic systems based on polyhedral boron clusters has the potential to solve challenging chemical problems such as the stabilization of reactive intermediates and transition-state-like species postulated for E–H (E = H, B, C, Si) bond activation reactions. We report on facile and clean B–H activation of a hydroborane by a new iridium boron cluster complex. The product of this reaction is an unprecedented and fully characterized transition metal-stabilized boron cation or borenium. Moreover, this intermediate bears an unusual intramolecular B···H interaction between the hydrogen originating from the activated hydroborane and the cyclometallated metal-bonded boron atom of the boron cluster. This B···H interaction is proposed to be an arrested insertion of hydrogen into the Bcage–metal bond and the initiation step for iridium “cage-walking” around the upper surface of the boron cluster. The “cage-walking” process is supported by the hydrogen–deuterium exchange observed at the boron cluster, and a mechanism is proposed on the basis of theoretical methods with a special focus on the role of noncovalent interactions. All new compounds were isolated and fully characterized by NMR spectroscopy and elemental analysis. Key compounds were studied by single crystal X-ray diffraction and X-ray photoelectron spectroscopy.

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Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Scopus Subject Areas:Physical Sciences > Catalysis
Physical Sciences > General Chemistry
Life Sciences > Biochemistry
Physical Sciences > Colloid and Surface Chemistry
Uncontrolled Keywords:Colloid and Surface Chemistry, Biochemistry, General Chemistry, Catalysis
Language:English
Date:12 October 2022
Deposited On:17 Oct 2022 11:25
Last Modified:28 May 2024 01:40
Publisher:American Chemical Society (ACS)
ISSN:0002-7863
OA Status:Green
Publisher DOI:https://doi.org/10.1021/jacs.2c06298
  • Content: Accepted Version
  • Language: English