Abstract
The reaction of Zintl phases K(3)As(7) and K(3)P(7) were investigated with 1-azido-4-bromobenzene (4-BrC(6)H(4)N(3)) and found to yield potassium salts of substituted diazadipnictogen rings (general molecular fragment {(RN)(2)Pn(2)}; Pn = P, As). In the case of the arsenic derivatives, amido-(imino)-arsenide persists in solution and bis-(amido)-diazadiarsenide persists in the solid state. These two species can be considered to share a monomer-dimer relationship, accessible by alteration between the solid and solution states, whereas in the case of K(3)P(7), our crystallographic and spectroscopic studies are consistent with the formation of a bisamido-(bisimino)-diazadiphosphenide, the "dimeric" form, persisting in both the solid and solution phase. Subsequent reactivity studies with amido-(imino)-arsenide show that it can act as a source of amide anion, giving a carbonate and a thiourea derivative when investigated with CO(2) and CS(2), respectively.