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Peer-reviewedCC BYThe journal of physical chemistry. A

Multicenter Bonding in Wilkinson's Catalyst: A Theoretical Study from a Distorted Monomer to a Localized Dimer.

  • Aleksandr Zaichenko1,2,3
  • Holger F Bettinger4
  • Ivana Fleischer4
  • Doreen Mollenhauer1,2,3
4 affiliations
  1. 1Helmholtz Institute for Polymers in Energy Applications Jena (HIPOLE Jena), Lessingstrasse 12-14, Jena07743, Germany.
  2. 2Helmholtz-Zentrum Berlin für Materialien Und Energie GmbH (HZB), Hahn-Meitner-Platz 1, Berlin14109, Germany.
  3. 3Institute for Technical and Environmental Chemistry, Friedrich Schiller University Jena, Philosophenweg 7a, Jena07743, Germany.
  4. 4Institut für Organische Chemie , Auf der Morgenstelle 18, Tübingen72076, Germany.
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Abstract

In this work, we present a computational study of Wilkinson's catalyst, [Rh(PPh3)3Cl], focusing on the connection between geometric structure, electronic structure, and thermodynamics in its monomeric and dimeric forms, as well as the coordination of hydrogen atoms. Scalar-relativistic DFT with modern meta-GGA-based functionals, coupled-cluster benchmarks, and bonding analyses (NBO/NRT) show that steric effects and noncovalent interactions control deviations from ideal square-planar geometry in the metastable monomeric structure as well as affect dissociation and dimerization energetics, whereas electronic factors dominate the dimer structure and enthalpy. The monomer is characterized by intrinsically delocalized multicenter bonding, best described as two crossed three-center, four-electron (3c-4e) interactions spanning Rh, while entropy-controlled dimerization induces a qualitatively different and more localized bonding regime. In both species, Rh acts as an electron acceptor in donor-acceptor Rh-ligand interactions and remains consistent with a 16-electron configuration. Thermodynamic results support the experimentally observed tendency toward dimerization in solution, highlighting the importance of multicenter bonding, entropic factors, and steric control for interpreting the structure and reactivity of Wilkinson's catalyst.

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Cite

BibTeXRIS
BibTeX
@article{zaichenko2026multicenter,
  title = {{Multicenter Bonding in Wilkinson's Catalyst: A Theoretical Study from a Distorted Monomer to a Localized Dimer.}},
  author = {Aleksandr Zaichenko and Holger F Bettinger and Ivana Fleischer and Doreen Mollenhauer},
  journal = {The journal of physical chemistry. A},
  year = {2026},
  month = oct,
  doi = {10.1021/acs.jpca.6c04219},
  url = {https://europepmc.org/article/MED/42917612},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - Multicenter Bonding in Wilkinson's Catalyst: A Theoretical Study from a Distorted Monomer to a Localized Dimer.
AU  - Aleksandr Zaichenko
AU  - Holger F Bettinger
AU  - Ivana Fleischer
AU  - Doreen Mollenhauer
PY  - 2026
DA  - 2026/10/01
JO  - The journal of physical chemistry. A
DO  - 10.1021/acs.jpca.6c04219
UR  - https://europepmc.org/article/MED/42917612
AB  - In this work, we present a computational study of Wilkinson's catalyst, [Rh(PPh3)3Cl], focusing on the connection between geometric structure, electronic structure, and thermodynamics in its monomeric and dimeric forms, as well as the coordination of hydrogen atoms. Scalar-relativistic DFT with modern meta-GGA-based functionals, coupled-cluster benchmarks, and bonding analyses (NBO/NRT) show that steric effects and noncovalent interactions control deviations from ideal square-planar geometry in the metastable monomeric structure as well as affect dissociation and dimerization energetics, whereas electronic factors dominate the dimer structure and enthalpy. The monomer is characterized by intrinsically delocalized multicenter bonding, best described as two crossed three-center, four-electron (3c-4e) interactions spanning Rh, while entropy-controlled dimerization induces a qualitatively different and more localized bonding regime. In both species, Rh acts as an electron acceptor in donor-acceptor Rh-ligand interactions and remains consistent with a 16-electron configuration. Thermodynamic results support the experimentally observed tendency toward dimerization in solution, highlighting the importance of multicenter bonding, entropic factors, and steric control for interpreting the structure and reactivity of Wilkinson's catalyst.
SN  - 1089-5639
SN  - 1520-5215
ER  -