Structure And Reactivity Of Alkaline Metal Bis(Amido)Diazadiarsetidinides

A series of alkaline metal functionalised tert-butyl substituted bis(amido)diazadiarsetidinides [(mu-N(tBu)As)(2)(N(tBu)M)(2)] (M=K (1), Rb (2), Cs (3), Na.thf (4), Na (5)) were prepared and their solid state structures investigated in detail. Further substitution reactions with tert-butyl substituted element chlorides of P, As, Sb and Bi were performed. The conversion of two equivalents tBu(2)AsCl (II) with 1-3 unexpectedly leads to the introduction of only one arsine moiety ([(mu-N(tBu)As)(2)(N(tBu)H)(N(tBu)AstBu(2)] (6)) while the other nitrogen atom gets protonated by ether cleavage. The reaction of one equivalent tBuECl(2) (E=As (III), Sb (IV)) with 1, 2 or 3 yielded the intended cage compounds [(mu-N(tBu)As)(2)(NtBu)(2)EtBu] (E=As (7), Sb (8)) in high yields. Reaction of 1-3 with two equivalents of tBu(2)E'Cl (E'=Sb (V), Bi (VI)) yields the twofold substituted bis(amido)diazadiarsetidines [(mu-N(tBu)As)(2)(N(tBu)E'tBu(2))(2)] (E'=Sb (9), Bi (10)), which show weak intramolecular E'-E' interactions.