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Characterization of bonding modes in metal complexes through electron density cross-sections.

Authors
  • de Beer, Shane1
  • Cukrowski, Ignacy1
  • de Lange, Jurgens H1
  • 1 Department of Chemistry, Faculty of Natural and Agricultural Sciences, University of Pretoria, Pretoria, South Africa. , (South Africa)
Type
Published Article
Journal
Journal of Computational Chemistry
Publisher
Wiley (John Wiley & Sons)
Publication Date
Dec 15, 2020
Volume
41
Issue
32
Pages
2695–2706
Identifiers
DOI: 10.1002/jcc.26423
PMID: 32956494
Source
Medline
Keywords
Language
English
License
Unknown

Abstract

Qualitative inspection of molecular orbitals (MOs) remains one of the most popular analysis tools used to describe the electronic structure and bonding properties of transition metal complexes. In symmetric coordination complexes, the use of group theory and the symmetry-adapted linear combination (SALC) of fragment orbitals allows for a very accurate and informative interpretation of MOs, but the same procedure cannot be performed for asymmetric complexes, such as Schrock and Fischer carbenes. In this work, we present a straight-forward approach for classifying and quantifying MO contributions to a particular metal-ligand interaction. Our approach utilizes the topology of MO density contributions to a cross-section of an inter-nuclear region, and is computationally inexpensive and applicable to symmetric and asymmetric complexes alike. We also apply the same approach with similar decompositions using Natural Bond Orbitals (NBO) and the recently developed Fragment, Atomic, Localized, Delocalized and Interatomic (FALDI) density decomposition scheme. In particular, FALDI analysis provides additional insights regarding the multi-centric nature of metal-carbene bonds without resorting to expensive multi-reference calculations. © 2020 Wiley Periodicals LLC.

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