Experimental and Theoretical Study of the Reactivity of Gold Nanoparticles Towards Benzimidazole‐2‐ylidene Ligands. Issue 30 (27th June 2016)

• Record Type: Journal Article
• Authors: Rodríguez‐Castillo, María; Lugo‐Preciado, Gustavo; Laurencin, Danielle; Tielens, Frederik; van der Lee, Arie; Clément, Sébastien; Guari, Yannick; López‐de‐Luzuriaga, José M.; Monge, Miguel; Remacle, Françoise; Richeter, Sébastien
• Is Part Of: Chemistry. Volume 22:Issue 30(2016)
• Page Start: 10446
• Page End: 10458
• Publication Date: 2016-06-27
• Subjects: carbenes -- DFT -- gold -- nanoparticles -- surface; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201601253
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The reactivity of benzimidazol‐2‐ylidenes with respect to gold nanoparticles (AuNPs) has been investigated using a combined experimental and computational approach. First, the grafting of benzimidazol‐2‐ylidenes bearing benzyl groups on the nitrogen atoms is described, and comparisons are made with structurally similar N‐heterocyclic carbenes (NHCs) bearing other N‐groups. Similar reactivity was observed for all NHCs, with 1) the erosion of the AuNPs under the effect of the NHC and 2) the formation of bis(NHC) gold complexes. DFT calculations were performed to investigate the modes of grafting of such ligands, to determine adsorption energies, and to rationalize the spectroscopic data. Two types of computational models were developed to describe the grafting onto large or small AuNPs, with either periodic or cluster‐type DFT calculations. Calculations of NMR parameters were performed on some of these models, and discussed in light of the experimental data. Abstract : Gold rush : A combined experimental and computational approach was used to investigate how the reaction between benzimidazol‐2‐ylidenes and gold nanoparticles (AuNPs) can afford molecular bis(carbene) gold complexes and grafted AuNPs (see figure). Periodic and cluster‐type DFT calculations were carried out, notably to calculate 13 C NMR spectra of surface‐modified nanoparticles for comparison with experimental data.