Cesium's Off-the-Map Valence Orbital

Maarten G. Goesten; Martin Rahm; F. Matthias Bickelhaupt; Emiel J.M. Hensen

doi:10.1002/anie.201704118

Cesium's Off-the-Map Valence Orbital

Maarten G. Goesten^*
, Martin Rahm
, F. Matthias Bickelhaupt
, Emiel J.M. Hensen

^*Corresponding author for this work

AIMMS

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

The T_d-symmetric [CsO₄]⁺ ion, featuring Cs in an oxidation state of 9, is computed to be a minimum. Cs uses outer core 5s and 5p orbitals to bind the oxygen atoms. The valence Cs 6s orbital lies too high to be involved in bonding, and contributes to Rydberg levels only. From a molecular orbital perspective, the bonding scheme is reminiscent of XeO₄: an octet of electrons to bind electronegative ligands, and no low-lying acceptor orbitals on the central atom. In this sense, Cs⁺ resembles hypervalent Xe.

Original language	English
Pages (from-to)	9772-9776
Number of pages	5
Journal	Angewandte Chemie International Edition in English
Volume	56
Issue number	33
DOIs	https://doi.org/10.1002/anie.201704118
Publication status	Published - 2 Aug 2017

Funding

We thank Prof. Dr. Roald Hoffmann for valuable discussion and analysis of the literature. This work is part of the Rubicon research programme with project number 019.161BT.031, which is (partly) financed by the Netherlands Organisation for Scientific Research (NWO).

Funders
Nederlandse Organisatie voor Wetenschappelijk Onderzoek

Keywords

bond theory
core electron reactivity
inorganic chemistry
oxidation
valence

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title = "Cesium's Off-the-Map Valence Orbital",

abstract = "The Td-symmetric [CsO4]+ ion, featuring Cs in an oxidation state of 9, is computed to be a minimum. Cs uses outer core 5s and 5p orbitals to bind the oxygen atoms. The valence Cs 6s orbital lies too high to be involved in bonding, and contributes to Rydberg levels only. From a molecular orbital perspective, the bonding scheme is reminiscent of XeO4: an octet of electrons to bind electronegative ligands, and no low-lying acceptor orbitals on the central atom. In this sense, Cs+ resembles hypervalent Xe.",

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AU - Goesten, Maarten G.

AU - Rahm, Martin

AU - Bickelhaupt, F. Matthias

AU - Hensen, Emiel J.M.

PY - 2017/8/2

Y1 - 2017/8/2

N2 - The Td-symmetric [CsO4]+ ion, featuring Cs in an oxidation state of 9, is computed to be a minimum. Cs uses outer core 5s and 5p orbitals to bind the oxygen atoms. The valence Cs 6s orbital lies too high to be involved in bonding, and contributes to Rydberg levels only. From a molecular orbital perspective, the bonding scheme is reminiscent of XeO4: an octet of electrons to bind electronegative ligands, and no low-lying acceptor orbitals on the central atom. In this sense, Cs+ resembles hypervalent Xe.

AB - The Td-symmetric [CsO4]+ ion, featuring Cs in an oxidation state of 9, is computed to be a minimum. Cs uses outer core 5s and 5p orbitals to bind the oxygen atoms. The valence Cs 6s orbital lies too high to be involved in bonding, and contributes to Rydberg levels only. From a molecular orbital perspective, the bonding scheme is reminiscent of XeO4: an octet of electrons to bind electronegative ligands, and no low-lying acceptor orbitals on the central atom. In this sense, Cs+ resembles hypervalent Xe.

KW - bond theory

KW - core electron reactivity

KW - inorganic chemistry

KW - oxidation

KW - valence

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JF - Angewandte Chemie International Edition in English

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ER -

Cesium's Off-the-Map Valence Orbital

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