Kraus, Florian and Korber, Nikolaus (2005) The chemical bond in polyphosphides: Crystal structures, the electron localization function, and a new view of aromaticity inP(4)(2-) and P-5(-). CHEMISTRY-A EUROPEAN JOURNAL, 11 (20). pp. 5945-5959. ISSN 0947-6539, 1521-3765
Full text not available from this repository. (Request a copy)Abstract
The incongruent solvation of (M4P6)-P-I species (M-I = K, Rb, Cs) in liquid ammonia leads to a broad variety of polyphosphides such as P-7(3-), P-11(3-), and the putatively aromatic P-4(2-) and P-5(-), which we investigated by using NMR spectroscopy and single-crystal X-ray structure analysis. The structures of Cs(2)P(4)(.)2NH(3), (K@[18]crown-6)(3)-K-3(P-7)(2)(.)10NH(3), Rb(3)P(7)(.)7NH(3), and (Rb@[18]crown-6)(3)P-7.6NH(3) are discussed and compared. The electron localization function ELF is used in a comparison of the chemical bonding of various phosphorus species. The variances of the basin populations provide a well-established measure for electron delocalization and therefore aromaticity. While comparable variance is calculated for P-4(2-) and P-5(-) it is observed in the lone pairs rather than in the basin populations of the bonds as in the prototypical aromatic hydrocarbons such as benzene or the cyclopentadienide anion. For this behavior, the term "lone pair aromaticity" is proposed.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | MOLECULAR-ORBITAL METHODS; GAUSSIAN-BASIS SETS; PENTAPHOSPHACYCLOPENTADIENIDE ION; TOPOLOGICAL ANALYSIS; POLYHEDRAL BORANES; PHOSPHORUS LIGANDS; WHITE PHOSPHORUS; LIQUID-AMMONIA; COMPLEX LIGAND; CHEMISTRY; aromaticity; ELF (electron localization function); liquid ammonia; polyphosphides; structure elucidation |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Nikolaus Korber |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 26 Apr 2021 06:38 |
| Last Modified: | 26 Apr 2021 06:38 |
| URI: | https://pred.uni-regensburg.de/id/eprint/35534 |
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