Help Privacy Policy Disclaimer
  Advanced SearchBrowse




Journal Article

Where Is the Fluoro Wall?: A Quantum Chemical Investigation


Rolfes,  Julian D.
Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;


van Gastel,  Maurice
Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;


Neese,  Frank
Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

External Resource
No external resources are shared
Fulltext (restricted access)
There are currently no full texts shared for your IP range.
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)
There is no public supplementary material available

Rolfes, J. D., van Gastel, M., & Neese, F. (2020). Where Is the Fluoro Wall?: A Quantum Chemical Investigation. Inorganic Chemistry, 59(2), 1556-1565. doi:10.1021/acs.inorgchem.9b03474.

Cite as: https://hdl.handle.net/21.11116/0000-0005-B12B-3
Despite their isoelectronic properties, fluoro and oxo ligands exhibit completely different chemical behavior. Formally speaking, the first is known to exclusively form single bonds, while the latter is generally observed to form double (or even triple) bonds. The biggest difference, however, lies in what is known among inorganic chemists as the Oxo Wall: the fact that six-coordinate tetragonal transition metal oxo complexes are not observed beyond group 7 elements. While the Oxo Wall was explained a few decades ago, some questions regarding the nature of the Oxo Wall remain unanswered. For example, why do group 8 oxo complexes with high oxidation states not violate the Oxo Wall? Moreover, why are transition metal fluoro complexes observed through the whole transition metal series? In order to understand how the small difference between these two isoelectronic ligands can give rise to such different chemical behaviors, we conducted an extensive computational analysis of the geometric and electronic properties of model fluoro and oxo complexes with metals around the Oxo Wall. Among many insights into the details of the Oxo Wall, we mostly learned that the oxygen 2p orbitals are prone to meaningfully interact with transition metal d orbitals, because they match not only spatially but also energetically, while for fluorine the p orbital energies are lower to an extent that interaction with transition metal d orbitals is much reduced. This in turn implies that in those instances where the metal d orbitals principally accessible for interaction are occupied, the oxygen 2p orbitals are too exposed to be stable.