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dc.contributor.authorAzofra, Luis Miguel
dc.contributor.authorVeenboer, Richard M. P.
dc.contributor.authorFalivene, Laura
dc.contributor.authorVummaleti, Sai V. C.
dc.contributor.authorpoater, albert
dc.contributor.authorNolan, Steven P.
dc.contributor.authorCavallo, Luigi
dc.date.accessioned2019-07-14T13:33:06Z
dc.date.available2019-07-14T13:33:06Z
dc.date.issued2019
dc.identifier.citationAzofra, L. M., Veenboer, R. M. P., Falivene, L., Vummaleti, S. V. C., Poater, A., Nolan, S. P., & Cavallo, L. (2019). Quantifying electronic similarities between NHC–gold(i) complexes and their isolobal imidazolium precursors. Physical Chemistry Chemical Physics, 21(28), 15615–15622. doi:10.1039/c9cp02844g
dc.identifier.doi10.1039/c9cp02844g
dc.identifier.urihttp://hdl.handle.net/10754/656011
dc.description.abstractA series of NHC–gold(I) (NHC = N-heterocyclic carbene) complexes has been studied by DFT calculations, enabling comparison of electronic and NMR behaviour with related protonated and free NHC molecules. Based on calculations, the NMR resonances of the carbenic C2 carbon atom in [Au(NHC)(Cl)] and [NHC(H)][Cl] exhibit increased shielding when compared to the free N-heterocyclic carbenes by an average of 46.6 ± 2.2 and 73.7 ± 4.3 ppm, respectively. A similar trend is observed when analysing the paramagnetic term of the magnetic shielding tensor. Although gold(I) and proton are considered isolobal fragments, imidazolium compounds lack π-backdonation due to the energetic unavailability of d-orbitals in H+. We propose that NHC–gold(I) complexes exhibit important π-backdonation irrespective of the relative amount of σ-donation between the NHC and gold(I)–X (X = anionic ligand) moieties in Au–NHC complexes. Interestingly, a correlation exists between the calculated shielding for gold (197Au) and the π-donation and π-backdonation contributions. We describe that this correlation also exists when analysing the σ-backdonation term, a property generally ignored yet representing a significant energetic contribution to the stability of the C2–Au bond.
dc.description.sponsorshipL. M. A. is an ULPGC Postdoc Fellow, and thanks Universidad de Las Palmas de Gran Canaria (ULPGC). L. F., S. V. C. V., S. P. N. and L. C. acknowledge King Abdullah University of Science and Technology (KAUST) for support. R. M. P. V. and S. P. N. thank the European Research Council (ERC). A. P. is a Serra Húnter Fellow, and thanks the MICINN for the project PGC2018-097722-B-I00. We also thank the KAUST Supercomputing Laboratory, housing the supercomputer Shaheen II, for providing computational resources.
dc.publisherRoyal Society of Chemistry (RSC)
dc.relation.urlhttp://xlink.rsc.org/?DOI=C9CP02844G
dc.rightsArchived with thanks to Physical Chemistry Chemical Physics
dc.titleQuantifying electronic similarities between NHC–gold(i) complexes and their isolobal imidazolium precursors
dc.typeArticle
dc.contributor.departmentChemical Science
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalPhysical Chemistry Chemical Physics
dc.rights.embargodate2020-07-14
dc.eprint.versionPost-print
dc.contributor.institutionCIDIA-FEAM (Unidad Asociada al Consejo Superior de Investigaciones Científicas, CSIC, avalada por el Instituto de Ciencia de Materiales de Sevilla, Universidad de Sevilla), Instituto de Estudios Ambientales y Recursos Naturales (i-UNAT), Universidad de Las Palmas de Gran Canaria (ULPGC), Campus de Tafira, Las Palmas de Gran Canaria, Spain
dc.contributor.institutionDepartamento de Química, Universidad de Las Palmas de Gran Canaria (ULPGC), Campus de Tafira, Las Palmas de Gran Canaria, Spain
dc.contributor.institutionEaStCHEM, School of Chemistry, University of St Andrews, North Haugh, St Andrews, UK
dc.contributor.institutionInstitut de Química Computacional i Catàlisi, Departament de Química, Universitat de Girona, c/M Aurèlia Capmany 69, 17003 Girona, Spain
dc.contributor.institutionDepartment of Chemistry and Center for Sustainable Chemistry, Ghent University, Building S3, Krijgslaan 281, 9000 Gent, Belgium
dc.contributor.institutionDepartment of Chemistry, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia
kaust.personVummaleti, Sai V. C.
kaust.personCavallo, Luigi
kaust.acknowledged.supportUnitSupercomputing Laboratory


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