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

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