Computational study of organo-cesium complexes and the possibility of lanthanide/actinide ions substitution

Walter A. Rabanal-León; Guillermo Martinez-Ariza; Sue A. Roberts; Christopher Hulme; Ramiro Arratia-Pérez

doi:10.1016/j.cplett.2015.10.048

Computational study of organo-cesium complexes and the possibility of lanthanide/actinide ions substitution

Walter A. Rabanal-León, Guillermo Martinez-Ariza, Sue A. Roberts, Christopher Hulme, Ramiro Arratia-Pérez

Research output: Contribution to journal › Article › peer-review

Abstract

Relativistic DFT calculations suggest that two organo-cesium complexes studied herein afford large HOMO-LUMO gaps of around 2.4 eV with the PBE xc-functional, which accounts for their stability. Energy decomposition studies suggest these two complexes are largely ionic with about 20% covalency. However, when the Cs⁺ ions are substituted by the isoelectronic La³⁺ and Th⁴⁺, their predicted ionicity decreases significantly. The significant increase in covalence indicates that employing Ugi reaction cascades that afford tetramic acid-based organo-cesium complexes may be extended to La³⁺ and Th⁴⁺ organometallics.

Original language	English (US)
Pages (from-to)	181-186
Number of pages	6
Journal	Chemical Physics Letters
Volume	641
DOIs	https://doi.org/10.1016/j.cplett.2015.10.048
State	Published - Nov 16 2015

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1016/j.cplett.2015.10.048

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title = "Computational study of organo-cesium complexes and the possibility of lanthanide/actinide ions substitution",

abstract = "Relativistic DFT calculations suggest that two organo-cesium complexes studied herein afford large HOMO-LUMO gaps of around 2.4 eV with the PBE xc-functional, which accounts for their stability. Energy decomposition studies suggest these two complexes are largely ionic with about 20% covalency. However, when the Cs+ ions are substituted by the isoelectronic La3+ and Th4+, their predicted ionicity decreases significantly. The significant increase in covalence indicates that employing Ugi reaction cascades that afford tetramic acid-based organo-cesium complexes may be extended to La3+ and Th4+ organometallics.",

author = "Rabanal-Le{\'o}n, {Walter A.} and Guillermo Martinez-Ariza and Roberts, {Sue A.} and Christopher Hulme and Ramiro Arratia-P{\'e}rez",

note = "Funding Information: G.M.A. is grateful for the financial support from CONACyT/UA doctoral scholarship 215981 (CVU: 464318) and Professors Denis Lichtenberger (UA), and Zhiping Zheng (UA) are acknowledged for useful discussions. R.A.P. is grateful for the financial support from Millennium Nucleus 120001 and Fondecyt 1150629 . W.A.R.L. acknowledges CONICYT/PCHA/Doctorado Nacional/2013 N° 63130118 for his Ph.D. fellowship. Publisher Copyright: {\textcopyright} 2015 Elsevier B.V.",

year = "2015",

month = nov,

day = "16",

doi = "10.1016/j.cplett.2015.10.048",

language = "English (US)",

volume = "641",

pages = "181--186",

journal = "Chemical Physics Letters",

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AU - Rabanal-León, Walter A.

AU - Martinez-Ariza, Guillermo

AU - Roberts, Sue A.

AU - Hulme, Christopher

AU - Arratia-Pérez, Ramiro

N1 - Funding Information: G.M.A. is grateful for the financial support from CONACyT/UA doctoral scholarship 215981 (CVU: 464318) and Professors Denis Lichtenberger (UA), and Zhiping Zheng (UA) are acknowledged for useful discussions. R.A.P. is grateful for the financial support from Millennium Nucleus 120001 and Fondecyt 1150629 . W.A.R.L. acknowledges CONICYT/PCHA/Doctorado Nacional/2013 N° 63130118 for his Ph.D. fellowship. Publisher Copyright: © 2015 Elsevier B.V.

PY - 2015/11/16

Y1 - 2015/11/16

N2 - Relativistic DFT calculations suggest that two organo-cesium complexes studied herein afford large HOMO-LUMO gaps of around 2.4 eV with the PBE xc-functional, which accounts for their stability. Energy decomposition studies suggest these two complexes are largely ionic with about 20% covalency. However, when the Cs+ ions are substituted by the isoelectronic La3+ and Th4+, their predicted ionicity decreases significantly. The significant increase in covalence indicates that employing Ugi reaction cascades that afford tetramic acid-based organo-cesium complexes may be extended to La3+ and Th4+ organometallics.

AB - Relativistic DFT calculations suggest that two organo-cesium complexes studied herein afford large HOMO-LUMO gaps of around 2.4 eV with the PBE xc-functional, which accounts for their stability. Energy decomposition studies suggest these two complexes are largely ionic with about 20% covalency. However, when the Cs+ ions are substituted by the isoelectronic La3+ and Th4+, their predicted ionicity decreases significantly. The significant increase in covalence indicates that employing Ugi reaction cascades that afford tetramic acid-based organo-cesium complexes may be extended to La3+ and Th4+ organometallics.

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JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -

Computational study of organo-cesium complexes and the possibility of lanthanide/actinide ions substitution

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