Syntheses and Structures of 5-Membered Heterocycles Featuring 1,2-Diphospha-1,3-Butadiene and Its Radical Anion

LGa(P2OC)cAAC 2 features a 1,2-diphospha-1,3-butadiene unit with a delocalized pi-type HOMO and a pi*-type LUMO according to DFT calculations. [LGa(P2OC)cAAC][K(DB-18-c-6)] 3[K(DB-18-c-6] containing the 1,2-diphospha-1,3-butadiene radical anion 3(center dot-) was isolated from the reaction of 2 with KC8 and dibenzo-18-crown-6. 3 reacted with [Fc][B(C6F5)(4)] (Fc=ferrocenium) to 2 and with TEMPO to [L-HGa(P2OC)cAAC][K(DB-18-c-6)] 4[K(DB-18-c-6] containing the 1,2-diphospha-1,3-butadiene anion 4(-). The solid state structures of 2, 3K(DB-18-c-6], and 4[K(DB-18-c-6] were determined by single crystal X-ray diffraction (sc-XRD).

Automated summary

LGa(P2OC)cAAC2 features a unique structure with conjugated HOMO and LUMO. Compounds containing 1,2-diphospha-1,3-butadiene radical and anion were obtained through reactions. The solid-state structures of these compounds were determined by X-ray diffraction.