- Titel
- Homoatomic cations
- Untertitel
- From [P₅]⁺ to [P₉]⁺
- Zitierfähige Url:
- https://nbn-resolving.org/urn:nbn:de:bsz:14-qucosa2-904306
- Quellenangabe
- Science advances
Erscheinungsjahr: 2022
Jahrgang: 8
Heft: 36
E-ISSN: 2375-2548
Artikelnummer: eabq8613 - Erstveröffentlichung
- 2022
- Abstract (EN)
- Recent synthetic approaches to a series of [P₉]X salts (X = [F{Al(ORꜰ)₃}₂], [Al(ORꜰ)₄], and (Rꜰ = C(CF₃)₃); Ga₂Cl₇) overcome limitations in classical synthesis methods that proved unsuitable for phosphorus cations. These salts contain the homopolyatomic cation [P₉]⁺ via (I) oxidation of P₄ with NO[F{Al(ORꜰ)₃}₂], (II) the arene-stabilized Co(I) sandwich complex [Co(arene)₂][Al(ORꜰ)₄] [arene = ortho-difluorobenzene (o-DFB) and fluorobenzene (FB)], or (III) the reduction of [P₅Cl₂][Ga₂Cl₇] with Ga[Ga₂Cl₇] as Ga(I) source in the presence of P₄. Quantum chemical CCSD(T) calculations suggest that [P₉]⁺ formation from [Co(arene)2]⁺ occurs via the nido-type cluster [(o-DFB)CoP₄]⁺, which resembles the isoelectronic, elusive [P₅]⁺. Apparently, the nido-cation [P₅]⁺ forms intermediately in all reactions, particularly during the Ga(I)-induced reduction of [P₅Cl₂]⁺ and the subsequent pick up of P₄ to yield the final salt [P₉][Ga₂Cl₇]. The solid-state structure of [P₉][Ga₂Cl₇] reveals the anticipated D₂d-symmetric Zintl-type cage for the [P₉]⁺ cation. Our approaches show great potential to bring other [Pn]⁺ cations from the gas to the condensed phase.
- Andere Ausgabe
- Link zum Artikel, der zuerst in „Science advances” erschienen ist.
DOI: 10.1126/sciadv.abq8613 - Freie Schlagwörter (DE)
- Oleumlösungen, nichtmetallische homopolyatomare Kationen, homoatomare Kationen, Synthese und Charakterisierung von [O₂][PtF₆]
- Freie Schlagwörter (EN)
- oleum solutions, nonmetallic homopolyatomic cations, homoatomic cations, synthesis and characterization of [O₂][PtF₆]
- Klassifikation (DDC)
- 500
- Verlag
- American Association for the Advancement of Science, Washington, DC [u.a.]
- Förder- / Projektangaben
- Deutsche Forschungsgemeinschaft (DFG)
ID: WE4621/3-1 und WE4621/3-2 - Deutsche Forschungsgemeinschaft (DFG)
ID: KR2046/26-2 - Deutsche Forschungsgemeinschaft (DFG)
ID: INST 40/467-1 - European Commission (EC)
FP7 | SP2 | ERC
Highly-Reactive (Regenerative) Phosphorus Building Blocks - New Concepts in Synthesis
(SYNPHOS)
ID: 307616 - Deutsche Forschungsgemeinschaft (DFG)
JUSTUS1 Cluster
ID: INST 40/467-1 - Deutsche Forschungsgemeinschaft (DFG)
JUSTUS2 Cluster
ID: 575-1 FUGG - Version / Begutachtungsstatus
- publizierte Version / Verlagsversion
- URN Qucosa
- urn:nbn:de:bsz:14-qucosa2-904306
- Veröffentlichungsdatum Qucosa
- 04.04.2024
- Dokumenttyp
- Artikel
- Sprache des Dokumentes
- Englisch
- Lizenz / Rechtehinweis
CC BY-NC 4.0