Synthesis and Reversible H2 Activation by Coordinatively Unsaturated Rhodium NHC Complexes
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Date
2023-04
Publication Type
Journal Article
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yes
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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.
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published
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Journal / series
Volume
106 (4)
Pages / Article No.
Publisher
Wiley‐VHCA
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Edition / version
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Date collected
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Subject
Coordinative unsaturation; Crystallography; Hydrogenation; N-Heterocyclic carbenes; Reversible H2 activation; Rhodium
Organisational unit
09634 - Morandi, Bill / Morandi, Bill
02024 - Small Molecule Crystallography Center
Notes
Funding
757608 - Shuttle Catalysis for Reversible Molecular Construction (EC)