Details

Autor(en) / Beteiligte

• Rottschäfer, Dennis
• Neumann, Beate
• Stammler, Hans-Georg
• Sergeieva, Tetiana
• Andrada, Diego M
• Ghadwal, Rajendra S

Titel

Isolation of a 16π-Electrons 1,4-Diphosphinine-1,4-diide with a Planar C 4 P 2 Ring

Ist Teil von

• Chemistry : a European journal, 2021-02, Vol.27 (9), p.3055-3064

Ort / Verlag

Germany

Erscheinungsjahr

2021

Quelle

Wiley Online Library

Beschreibungen/Notizen

• Herein, we report the first 1,4-diphosphinine-1,4-diide compound [(ADC )P] (5-Ph) (ADC =PhC{(NDipp)C} ; Dipp=2,6-iPr C H ) derived from an anionic dicarbene (ADC ) as a red crystalline solid. Compound 5-Ph containing a 16π-electron planar fused-tricyclic ring system was obtained by the 4e reduction of [(ADC )PCl ] (4-Ph) with Mg (or KC ) in a quantitative yield. Experimental and computational results imply that the central 8π-electrons C P ring of 5-Ph, which is fused between two 6π-electrons C N 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 P ring, while the second resides in a σ-symmetric orbital. This can be shown with the gold complex [(ADC )P(AuCl) ] (6-Ph) obtained by reacting 5-Ph with (Me S)AuCl. A mixture of 5-Ph and 4-Ph undergoes comproportionation in the presence of MgCl to form the intermediate oxidation state compound [(ADC )P] (MgCl ) (7-Ph), which is an aromatic species.