Bis(acyl)phosphide ‐ Ambidentate Ligands for the Synthesis of Group 14 and 15 Main Group Element Compounds

Abstract

AbstractThe 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 κ2‐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 E−P bonds is favoured over κ2‐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.