Jump to main content
Jump to site search

Issue 16, 2013
Previous Article Next Article

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

Author affiliations

Abstract

The Nδ,Nε-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*)Cl2), 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 SMet,CHis*-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.

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

Back to tab navigation

Supplementary files

Publication details

The article was received on 04 Nov 2012, accepted on 15 Feb 2013 and first published on 18 Feb 2013


Article type: Paper
DOI: 10.1039/C3DT50424G
Citation: Dalton Trans., 2013,42, 5655-5660
  •   Request permissions

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

    A. Monney, F. Nastri and M. Albrecht, Dalton Trans., 2013, 42, 5655
    DOI: 10.1039/C3DT50424G

Search articles by author

Spotlight

Advertisements