TY - JOUR
T1 - Computational study of organo-cesium complexes and the possibility of lanthanide/actinide ions substitution
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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U2 - 10.1016/j.cplett.2015.10.048
DO - 10.1016/j.cplett.2015.10.048
M3 - Article
AN - SCOPUS:84947772436
SN - 0009-2614
VL - 641
SP - 181
EP - 186
JO - Chemical Physics Letters
JF - Chemical Physics Letters
ER -