Issue 16, 2013
From the journal:

Dalton Transactions

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

Angèle Monney,a   Flavia Nastrib  and  Martin Albrecht*a  

* Corresponding authors

a School of Chemistry and Chemical Biology, University College Dublin, Belfield, Dublin 4, Ireland
E-mail: martin.albrecht@ucd.ie
Fax: +353 1716 2501
Tel: +353 1716 2504

b Department of Chemistry, University Federico II of Napoli, Complesso Universitario Monte S. Angelo, Via Cintia 45, 80126 Napoli, Italy

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

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Article information

DOI
https://doi.org/10.1039/C3DT50424G
Article type
Paper
Submitted
04 Nov 2012
Accepted
15 Feb 2013
First published
18 Feb 2013

Dalton Trans., 2013,42, 5655-5660

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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

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