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  Orbital Decomposition of the Carbon Chemical Shielding Tensor in Gold(I) N‐Heterocyclic Carbene Complexes

Izquierdo, M. A., Tarantelli, F., Broer, R., Bistoni, G., Belpassi, L., & Havenith, R. W. A. (2020). Orbital Decomposition of the Carbon Chemical Shielding Tensor in Gold(I) N‐Heterocyclic Carbene Complexes. European Journal of Inorganic Chemistry, 2020(13), 1177-1183. doi:10.1002/ejic.201901115.

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 Creators:
Izquierdo, Maria A.1, 2, Author
Tarantelli, Francesco3, 4, Author
Broer, Ria1, Author
Bistoni, Giovanni5, Author              
Belpassi, Leonardo4, Author
Havenith, Remco W. A.1, 6, 7, Author
Affiliations:
1Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands, ou_persistent22              
2Institute of Molecular Science, University of Valencia, P.O. Box 22085, 46071 Valencia, Spain, ou_persistent22              
3Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia, Via Elce di Sotto 8, 06123 Perugia, Italy, ou_persistent22              
4Istituto di Scienze e Tecnologie Chimiche del CNR “G. Natta” (SCITEC‐CNR), Via Elce di Sotto 8, 06123 Perugia, Italy, ou_persistent22              
5Research Group Bistoni, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541703              
6Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands, ou_persistent22              
7Ghent Quantum Chemistry Group, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281 (S3), B, ‐9000 Gent, Belgium, ou_persistent22              

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Free keywords: Carbene ligands; Gold; Chemical shielding tensor; Electron donation; Electron back-donation
 Abstract: The good performance of N‐heterocyclic carbenes (NHCs), in terms of versatility and selectivity, has called the attention of experimentalists and theoreticians attempting to understand their electronic properties. Analyses of the Au(I)–C bond in [(NHC)AuL]+/0 (L stands for a neutral or negatively charged ligand), through the Dewar–Chatt–Duncanson model and the charge displacement function, have revealed that NHC is not purely a σ‐donor but may have a significant π‐acceptor character. It turns out, however, that only the σ‐donation bonding component strongly correlates with one specific component of the chemical shielding tensor. Here, in extension to earlier works, a current density analysis, based on the continuous transformation of the current density diamagnetic zero approach, along a series of [(NHC)AuL]+/0 complexes is presented. The shielding tensor is decomposed into orbital contributions using symmetry considerations together with a spectral analysis in terms of occupied to virtual orbital transitions. Analysis of the orbital transitions shows that the induced current density is largely influenced by rotational transitions. The orbital decomposition of the shielding tensor leads to a deeper understanding of the ligand effect on the magnetic response properties and the electronic structure of (NHC)‐Au fragments. Such an orbital decomposition scheme may be extended to other magnetic properties and/or substrate‐metal complexes.

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Language(s): eng - English
 Dates: 2019-10-172020-03-122020-04-07
 Publication Status: Published in print
 Pages: 7
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/ejic.201901115
 Degree: -

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Title: European Journal of Inorganic Chemistry
  Abbreviation : Eur. J. Inorg. Chem.
Source Genre: Journal
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Publ. Info: Weinheim, Germany : Wiley-VCH
Pages: - Volume / Issue: 2020 (13) Sequence Number: - Start / End Page: 1177 - 1183 Identifier: ISSN: 1434-1948
CoNE: https://pure.mpg.de/cone/journals/resource/954926953810_1