Salt metathesis reactions between ethylenediamine (en) solutions of the K(3)E(7) (E = P, As) Zintl phases and post-transition metal halides (InCl(3), TlCl, SnI(2) and PbI(2)) have yielded a family of novel heteroatomic cluster anions, [In(E(7))(2)](3-), [TlE(7)](2-) and [E'E(15)](3-) (E' = Sn, Pb; E = P, As). Several of these new species have been characterized by single-crystal X-ray diffraction as salts of sequestered potassium cations in [K(2,2,2-crypt)](3)[In(P(7))(2)]·3.5py (1), [K(2,2,2-crypt)](2)[TlP(7)]·py (3), [K(18-crown-6)](2)[TlAs(7)] (4b), [K(2,2,2-crypt)](3)[E'P(15)]·en (E' = Sn (5), Pb (6)) and [K(2,2,2-crypt)](3)[SnAs(15)]·2en (7). The presence of all of the cluster anions in solution was confirmed by electrospray mass-spectrometry and by (1)H and (31)P{(1)H} NMR spectroscopy when pertinent.
