LAUSR

The reactivity of the bis(acyl)phosphide ion [P(COR)2]- (BAP-, R = Ph, Mes) with silicon halides SiX4 (X = Cl, Br) and pnictogen chlorides ECl3 (E = As, Sb and Bi) was investigated. The reaction with SiX4 leads to the hexacoordinate silanes SiX2(BAP)2 in which BAP- is coordinated in the chelating k2-O,O' mode, analogously to acac-. Unexpectedly, the coordination behaviour of BAP- differs from the one of acac- in the interpnictogen compounds E(BAP)3 (E = As, Sb) in which the formation of a E-P bonds is favoured over k2-O,O' chelation via the oxygen centres. Finally, the reaction of BiCl3 with three equivalents of Na(BAP) leads to the formation of red, crystalline Bi2(BAP)4, an air stable dibismuthine, as product of a redox reaction.