Isolation of a 16pi-Electrons 1,4-Diphosphinine-1,4-diide with a Planar C4P2 Ring

Rottschäfer D, Neumann B, Stammler H-G, Andrada D, Sergeieva T, Ghadwal R (2021)
Chemistry - A European Journal 27(9): 3055-3064.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
Herein, we report the first 1,4-diphosphinine-1,4-diide compound [(ADC Ph )P] 2 ( 5-Ph ) (ADC Ph = PhC{(NDipp)C} 2 ; Dipp = 2,6-iPr 2 C 6 H 3 ) derived from an anionic dicarbene (ADC Ph ) as a red crystalline solid. Compound 5-Ph containing a 16pi-electron planar fused-tricyclic ring system was obtained by the 4e reduction of [(ADC Ph )PCl 2 ] 2 ( 4-Ph ) with Mg (or KC 8 ) in a quantitative yield. Experimental and computational results imply that the central 8pi-electrons C 4 P 2 ring of 5-Ph , which is fused between two 6pi-electrons C 3 N 2 aromatic rings, is antiaromatic. Thus, each of the phosphorus atoms of 5-Ph has two electron-lone-pairs, one in a p-type orbital is in conjugation with the C=C bonds of the C 4 P 2 ring, while the second resides in a sigma-symmetric orbital. This can be shown with the gold complex [(ADC Ph )P(AuCl) 2 ] 2 ( 6-Ph ) obtained by reacting 5-Ph with (Me 2 S)AuCl. A mixture of 5-Ph and 4-Ph undergoes comproportionation in the presence of MgCl 2 to form the intermediate oxidation state compound [(ADC Ar )P] 2 (MgCl 4 ) ( 7-Ph ), which is an aromatic species. © 2020 Wiley-VCH GmbH.
Erscheinungsjahr
2021
Zeitschriftentitel
Chemistry - A European Journal
Band
27
Ausgabe
9
Seite(n)
3055-3064
eISSN
1521-3765
Finanzierungs-Informationen
Open-Access-Publikationskosten wurden durch die Universität Bielefeld im Rahmen des DEAL-Vertrags gefördert.
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https://pub.uni-bielefeld.de/record/2948418

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Rottschäfer D, Neumann B, Stammler H-G, Andrada D, Sergeieva T, Ghadwal R. Isolation of a 16pi-Electrons 1,4-Diphosphinine-1,4-diide with a Planar C4P2 Ring. Chemistry - A European Journal. 2021;27(9):3055-3064.
Rottschäfer, D., Neumann, B., Stammler, H. - G., Andrada, D., Sergeieva, T., & Ghadwal, R. (2021). Isolation of a 16pi-Electrons 1,4-Diphosphinine-1,4-diide with a Planar C4P2 Ring. Chemistry - A European Journal, 27(9), 3055-3064. https://doi.org/10.1002/chem.202003617
Rottschäfer, D., Neumann, B., Stammler, H. - G., Andrada, D., Sergeieva, T., and Ghadwal, R. (2021). Isolation of a 16pi-Electrons 1,4-Diphosphinine-1,4-diide with a Planar C4P2 Ring. Chemistry - A European Journal 27, 3055-3064.
Rottschäfer, D., et al., 2021. Isolation of a 16pi-Electrons 1,4-Diphosphinine-1,4-diide with a Planar C4P2 Ring. Chemistry - A European Journal, 27(9), p 3055-3064.
D. Rottschäfer, et al., “Isolation of a 16pi-Electrons 1,4-Diphosphinine-1,4-diide with a Planar C4P2 Ring”, Chemistry - A European Journal, vol. 27, 2021, pp. 3055-3064.
Rottschäfer, D., Neumann, B., Stammler, H.-G., Andrada, D., Sergeieva, T., Ghadwal, R.: Isolation of a 16pi-Electrons 1,4-Diphosphinine-1,4-diide with a Planar C4P2 Ring. Chemistry - A European Journal. 27, 3055-3064 (2021).
Rottschäfer, Dennis, Neumann, Beate, Stammler, Hans-Georg, Andrada, Diego, Sergeieva, Tetiana, and Ghadwal, Rajendra. “Isolation of a 16pi-Electrons 1,4-Diphosphinine-1,4-diide with a Planar C4P2 Ring”. Chemistry - A European Journal 27.9 (2021): 3055-3064.
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