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

ABSTRACT

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 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.