title: Experimental and Theoretical Study of the Reactivity of Gold Nanoparticles Towards Benzimidazole-2-ylidene Ligands.
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.
authors.affiliation: Institut Charles Gerhardt, UMR 5253 CNRS-ENSCM-UM, CC 1701, Université de Montpellier, Place E. Bataillon, 34095, Montpellier Cedex 05, France.
authors.forename: María
authors.initials: M
authors.lastname: Rodríguez-Castillo
authors.affiliation: Chemistry Department, B6c, University of Liège, 4000, Liège, Belgium.
authors.forename: Gustavo
authors.initials: G
authors.lastname: Lugo-Preciado
authors.affiliation: Institut Charles Gerhardt, UMR 5253 CNRS-ENSCM-UM, CC 1701, Université de Montpellier, Place E. Bataillon, 34095, Montpellier Cedex 05, France.
authors.forename: Danielle
authors.initials: D
authors.lastname: Laurencin
authors.affiliation: Sorbonne Université, UPMC Université Paris 06, UMR 7574, Laboratoire Chimie de la Matière Condensée de Paris, Collège de France, 11 place M. Berthelot, 7523, Paris Cedex 05, France. frederik.tielens@upmc.fr.
authors.forename: Frederik
authors.initials: F
authors.lastname: Tielens
authors.affiliation: Institut Européen des Membranes, UMR 5635 CNRS-ENSCM-UM, Université de Montpellier, Place E. Bataillon, 34095, Montpellier Cedex 05, France.
authors.forename: Arie
authors.initials: A
authors.lastname: van der Lee
authors.affiliation: Institut Charles Gerhardt, UMR 5253 CNRS-ENSCM-UM, CC 1701, Université de Montpellier, Place E. Bataillon, 34095, Montpellier Cedex 05, France.
authors.forename: Sébastien
authors.initials: S
authors.lastname: Clément
authors.affiliation: Institut Charles Gerhardt, UMR 5253 CNRS-ENSCM-UM, CC 1701, Université de Montpellier, Place E. Bataillon, 34095, Montpellier Cedex 05, France.
authors.forename: Yannick
authors.initials: Y
authors.lastname: Guari
authors.affiliation: Departamento de Química, Grupo de Síntesis Química de la Rioja, UA-CSIC, Complejo Científico-Tecnológico, Universidad de La Rioja, 26004, Logroño, Spain.
authors.forename: José M
authors.initials: JM
authors.lastname: López-de-Luzuriaga
authors.affiliation: Departamento de Química, Grupo de Síntesis Química de la Rioja, UA-CSIC, Complejo Científico-Tecnológico, Universidad de La Rioja, 26004, Logroño, Spain.
authors.forename: Miguel
authors.initials: M
authors.lastname: Monge
authors.affiliation: Chemistry Department, B6c, University of Liège, 4000, Liège, Belgium. fremacle@ulg.ac.be.
authors.forename: Françoise
authors.initials: F
authors.lastname: Remacle
authors.affiliation: Institut Charles Gerhardt, UMR 5253 CNRS-ENSCM-UM, CC 1701, Université de Montpellier, Place E. Bataillon, 34095, Montpellier Cedex 05, France. sebastien.richeter@umontpellier.fr.
authors.forename: Sébastien
authors.identifier: http://orcid.org/0000-0001-5284-0931
authors.initials: S
authors.lastname: Richeter
keywords: DFT; carbenes; gold; nanoparticles; surface