JACS [LCSOM]

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 transition7 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.

 

 

Reference :

Mustapha Hamdaoui, Fan Liu, Yann Cornaton, Xingyu Lu, Xiaohuo Shi, Huan Zhang, Jiyong Liu, Bernhard Spingler, Jean-Pierre Djukic, Simon Duttwyler

An Iridium-Stabilized Borenium Intermediate

Journal of the American Chemical Society -  DOI : 10.1021/jacs.2c06298 - JACS's TWeet

JACS's TWeet

Contact :

Jean-Pierre Djukic, team LCSOM, Institut de Chimie (UMR 7177).