The synthesis, structure, and reactions of (acylimino) triaryl-λ5-bismuthanes and a comparative study of the structure and reactivity of a series of (acylimino) pnictoranes are reported. Treatment of ortho-substituted triarylbismuth dichlorides 1 (Ar3BiCl2; Ar= 2- MeC6H4, 2-MeOC6H4, 2, 4, 6-Me3C6H2) with amides 2 (H2NCOR; R= CF3, CCl3, 3, 5- (CF3) 2C6H3) in the presence of 2.2 equiv of KO-t-Bu in dichloromethane afforded ( ...