Peptide-tethered monodentate and chelating histidylidene metal complexes: synthesis and application in catalytic hydrosilylation

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Title: Peptide-tethered monodentate and chelating histidylidene metal complexes: synthesis and application in catalytic hydrosilylation
Authors: Monney, Angèle
Nastri, Flavia
Albrecht, Martin
Permanent link: http://hdl.handle.net/10197/6596
Date: 28-Apr-2013
Abstract: The N-delta,N-epsilon-dimethylated histidinium salt (His*) was tethered to oligopeptides and metallated to form Ir(III) and Rh(I) NHC complexes. Peptide-based histidylidene complexes containing only alanine, Ala-Ala-His*-[M] and Ala-Ala-Ala-His*-[M] were synthesised ([M] = Rh(cod) Cl, Ir(Cp*)Cl-2), as well as oligopeptide complexes featuring a potentially chelating methionine and tyrosine residue, Met-Ala-Ala-His*-Rh(cod)Cl and Tyr-Ala-Ala-His*-Rh(cod)Cl. Chelation of the methionine-containing histidylidene ligand was induced by halide abstraction from the rhodium centre, while tyrosine remained non-coordinating under identical conditions. High catalytic activities in hydrosilylation were achieved with all peptide-based rhodium complexes. The cationic S-Met,C-His*-bidentate peptide rhodium catalyst outperformed the monodentate neutral peptide complexes and constitutes one of the most efficient rhodium carbene catalysts for hydrosilylation, providing new opportunities for the use of peptides as N-heterocyclic carbene ligands in catalysis.
Funding Details: European Research Council
Type of material: Journal Article
Publisher: Royal Society of Chemistry
Journal: Dalton Transactions
Volume: 42
Issue: 16
Start page: 5655
End page: 5660
Copyright (published version): 2013 The Royal Society of Chemistry
Keywords: N-heterocyclic carbenesChiral ionic liquidsAmino-acidEnantioselective catalysisArtificial metalloenzymesCombinatorial librariesLigandsRhodiumChemistryKetones
DOI: 10.1039/c3dt50424g
Language: en
Status of Item: Peer reviewed
Appears in Collections:Chemistry Research Collection

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