Asterane

Musso, Hans

doi:10.1002/ange.19680800720

Cited by 3 publications

(1 citation statement)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The three asteranes − examined also exhibit relatively large electron affinities, with that of perfluoro[5]asterane (OLYP: 2.43 eV) and perfluoro[4]asterane (2.03 eV) greatly exceeding that of perfluoro[3]asterane (1.36 eV). Again, there appears to be a pronounced size effect.…”

Section: Resultsmentioning

confidence: 99%

The Perfluoro Cage Effect: A Search for Electron-Encapsulating Molecules

Ghosh

Conradie

2023

ACS Omega

View full text Add to dashboard Cite

Quantum chemical calculations have for some time predicted that perfluorinated polyhedral organic molecules should exhibit a low-energy LUMO consisting of the overlapping inward-pointing lobes of the C−F σ* orbitals. Accordingly, these molecules should be able to encapsulate an electron within the interior of their cavities. Inspired by the recent confirmation of this prediction for perfluorocubane, we have sought to identify additional perfluorinated cage molecules capable of this remarkable behavior, which we refer to as the perfluoro cage effect (PCE). Using DFT calculations with multiple well-tested exchange-correlation functionals and large STO-QZ4P basis sets, we have identified several systems including [n]prismanes (n = 3−6), [n]asteranes (n = 3−5), twistane, and two norbornadiene dimer cages that clearly exhibit the PCE. In other words, they exhibit a low-energy LUMO belonging to the total symmetric irreducible representation of the point group in question and adiabatic electron affinities ranging from somewhat under 1 eV to over 2 eV. A pronounced size effect appears to hold, with larger cages exhibiting higher electron affinities (EAs). The largest adiabatic EAs, well over 3 eV, are predicted for perfluorinated dodecahedrane and C 60 . In contrast, the PCE is barely discernible for perfluorinated tetrahedrane and bicyclo[1.1.1]pentane.

show abstract

Section: Resultsmentioning

confidence: 99%

The Perfluoro Cage Effect: A Search for Electron-Encapsulating Molecules

Ghosh

Conradie

2023

ACS Omega

View full text Add to dashboard Cite

show abstract

Desaminierungsreaktionen, 23. Umlagerungen von Tricyclo[3.2.2.0 ^2,4 ]nonan‐Derivaten

Kirmse

Wahl

1974

Chem. Ber.

View full text Add to dashboard Cite

The decomposition of tricyclo[3.2.2.02~4]nonane-6-diazonium ions 20 ( e m ) and 22 (endo) has been studied to elucidate the effect of neighbouring cyclopropyl in deamination reactions. In contrast to the solvolysis of the corresponding sulfonate 49 no products indicating participation of the cyclopropane ring were obtained from 20. Direct displacement with retention of configuration was the major reaction of 20 whereas Wagner-Meerwein rearrangement predominated with 22. The endo-configuration of the major product 25 obtained from 22 must be attributed to the cyclopropylcarbinyl structure df the rearranged cation 56. The tricyclo[3.2.2.02~4]non-8-ene-6-diazonium ions 57 (endo) and 69 ( e m ) differed substantially in behavior from their saturated analogues. 57 produced tetracyclic products (e. g., 58) almost exclusively. 69 preferred the 5.6-shift of C-4, leading to an ally1 cation 78, but also showed some leakage to products of the type of 58.Der Zerfall aliphatischer Diazonium-Ionen bedarf wegen seiner geringen Aktivierungsenergie der Unterstiitzung durch Nachbargruppen weit weniger als die Solvolyse von Sulfonsaureestern oder Halogeniden. Das Studium v o n Nachbargruppen-Effekten ist daher besonders geeignet, Stickstoff als Abgangsgruppe naher zu charakterisieren. Wir berichten hier iiber eine derartige Untersuchung a n Tricyclo-[3.2.2.0 z.41nonan-Derivaten.

show abstract

Neue arsinidenverbrückte Mehrkern‐Clusterkomplexe des Ag und Au. Die Kristallstrukturen von [Ag₁₄(AsPh)₆Cl₂(PR₃)₈], (PR₃ = PEt₃, PMeⁿPr₂, PⁿPr₃), [M₄(As₄Ph₄)₂(PR₃)₄], (M = Ag, PR₃ = PEt₃, PⁿPr₃; M = Au, PR₃ = PⁿPr₃), [A

Fenske¹,

Simon²

1996

Zeitschrift anorg allge chemie

View full text Add to dashboard Cite

Bei der Reaktion von AgCl mit PhAs(SiMe3)2 bilden sich in Gegenwart der tertiären Phosphane PEt3, PMenPr2 und PnPr3 die Silbercluster der Zusammensetzung [Ag14(AsPh)6Cl2(PR3)8] (PR3 = PEt3 1, PMenPr2 2, PnPr3 3). Ferner konnten die Mehrkernkomplexe [Ag4(As4Ph4)2(PR3)4] (PR3 = PEt3 4, PMenPr2 5) isoliert werden. Bei analogen Umsetzungen von [PMe3AuCl] mit PhAs(SiMe3)2 und von PnPr3 bildet sich neben dem zu 4 und 5 isostrukturellen Goldkomplex [Au4(As4Ph4)2(PnPr3)4] 6 ein Goldcluster der Zusammensetzung [Au10(AsPh)4(PhAsSiMe3)2(PnPr3)6] 7. Die Strukturen von 1–7 konnten durch Kristallstrukturanalysen aufgeklärt werden. (1: Raumgruppe Pccn, a = 2 239,3(5) pm, b = 2 230,0(5) pm, c = 2 291,6(6) pm; 2: Raumgruppe P21/n, a = 1 703,1(9) pm, b = 2 241,0(20) pm, c = 1 730,8(14) pm, β = 98,79(4)°; 3: Raumgruppe P21/n, a = 1 741,8(3) pm, b = 2 260,0(9) pm, c = 1 867,5(5) pm, β = 94,63(2)°; 4: Raumgruppe P1, a = 1 535,2(4) pm, b = 1 599,3(3) pm, c = 1 644,5(5) pm, α = 90,90(2)°, β = 93,54(2)°, γ = 89,98(2)°; 5: Raumgruppe P1, a = 1 336,0(5) pm, b = 1 371,0(7) pm, c = 1 477,0(4) pm, α = 117,03(3)°, β = 93,93(2)°, γ = 103,82(3)°; 6: Raumgruppe P21/n, a = 1 305,9(2) pm, b = 2 227,1(3) pm, c = 1 619,6(4) pm, β = 108,38(2)°; 7: Raumgruppe 12, a = 1 948,5(3) pm, b = 1 638,9(5) pm, c = 2 148,7(4) pm, β = 94,93(1)°.

show abstract

Asterane

Cited by 3 publications

References 3 publications

The Perfluoro Cage Effect: A Search for Electron-Encapsulating Molecules

The Perfluoro Cage Effect: A Search for Electron-Encapsulating Molecules

Desaminierungsreaktionen, 23. Umlagerungen von Tricyclo[3.2.2.0 ^2,4 ]nonan‐Derivaten

Neue arsinidenverbrückte Mehrkern‐Clusterkomplexe des Ag und Au. Die Kristallstrukturen von [Ag₁₄(AsPh)₆Cl₂(PR₃)₈], (PR₃ = PEt₃, PMeⁿPr₂, PⁿPr₃), [M₄(As₄Ph₄)₂(PR₃)₄], (M = Ag, PR₃ = PEt₃, PⁿPr₃; M = Au, PR₃ = PⁿPr₃), [A

Contact Info

Product

Resources

About

Asterane

Cited by 3 publications

References 3 publications

The Perfluoro Cage Effect: A Search for Electron-Encapsulating Molecules

The Perfluoro Cage Effect: A Search for Electron-Encapsulating Molecules

Desaminierungsreaktionen, 23. Umlagerungen von Tricyclo[3.2.2.0 2,4 ]nonan‐Derivaten

Neue arsinidenverbrückte Mehrkern‐Clusterkomplexe des Ag und Au. Die Kristallstrukturen von [Ag14(AsPh)6Cl2(PR3)8], (PR3 = PEt3, PMenPr2, PnPr3), [M4(As4Ph4)2(PR3)4], (M = Ag, PR3 = PEt3, PnPr3; M = Au, PR3 = PnPr3), [A

Contact Info

Product

Resources

About

Desaminierungsreaktionen, 23. Umlagerungen von Tricyclo[3.2.2.0 ^2,4 ]nonan‐Derivaten

Neue arsinidenverbrückte Mehrkern‐Clusterkomplexe des Ag und Au. Die Kristallstrukturen von [Ag₁₄(AsPh)₆Cl₂(PR₃)₈], (PR₃ = PEt₃, PMeⁿPr₂, PⁿPr₃), [M₄(As₄Ph₄)₂(PR₃)₄], (M = Ag, PR₃ = PEt₃, PⁿPr₃; M = Au, PR₃ = PⁿPr₃), [A