Synthesis and Reversible H2 Activation by Coordinatively Unsaturated Rhodium NHC Complexes
Open access
Date
2023-04Type
- Journal Article
Abstract
We report the synthesis of coordinatively unsaturated cationic rhodium complexes bearing the sterically encumbered electron-rich NHC ligand IPr*OMe. The COD (1,5-cyclooctadiene) complex [Rh(IPr*OMe)(COD)]BF4 adopts a tilted, pseudo-square planar coordination geometry, where bonding to the ipso-carbon of the NHC aryl substituent was observed in the solid state. Hydrogenation of this complex afforded a metastable dihydride complex [Rh(IPr*OMe)(H)2]BF4 with an unusual internal coordination to an arene of the ligand. In the absence of a hydrogen atmosphere, spontaneous reductive elimination of H2 afforded a rhodium complex [Rh(IPr*OMe)]BF4 with a single chelating ligand that stabilizes the highly unsaturated metal by two-fold π-face donation as suggested by NMR spectroscopy and computational studies. This unusual complex might serve as a versatile precatalyst for a variety of transformations. Show more
Permanent link
https://doi.org/10.3929/ethz-b-000604759Publication status
publishedExternal links
Journal / series
Helvetica Chimica ActaVolume
Pages / Article No.
Publisher
Wiley-VCHSubject
Coordinative unsaturation; Crystallography; Hydrogenation; N-Heterocyclic carbenes; Reversible H2 activation; RhodiumOrganisational unit
09634 - Morandi, Bill / Morandi, Bill
02024 - Small Molecule Crystallography Center
Funding
757608 - Shuttle Catalysis for Reversible Molecular Construction (EC)
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