Distannabarrelenes with Three Coordinated Sn(II) Atoms

Crystalline 1,4‐distannabarrelene compounds [(ADC(Ar))(3)Sn(2)]SnCl(3) (3‐Ar) (ADC(Ar)={ArC(NDipp)(2)CC}; Dipp=2,6‐iPr(2)C(6)H(3), Ar=Ph or DMP; DMP=4‐Me(2)NC(6)H(4)) derived from anionic dicarbenes Li(ADC(Ar)) (2‐Ar) (Ar=Ph or DMP) have been reported. The cationic moiety of 3‐Ar features a barrelene framework with three coordinated Sn(II) atoms at the 1,4‐positions, whereas the anionic unit SnCl(3) is formally derived from SnCl(2) and chloride ion. The all carbon substituted bis‐stannylenes 3‐Ar have been characterized by NMR spectroscopy and X‐ray diffraction. DFT calculations reveal that the HOMO of 3‐Ph (ϵ=−6.40 eV) is mainly the lone‐pair orbital at the Sn(II) atoms of the barrelene unit. 3‐Ar readily react with sulfur and selenium to afford the mixed‐valence Sn(II)/Sn(IV) compounds [(ADC(Ar))(3)SnSn(E)](SnCl(6))(0.5) (E=S 4‐Ar, Ar=Ph or DMP; E=Se 5‐Ph).