Reactivity studies of group 15 Zintl ions towards homoleptic post-transition metal organometallics: a 'bottom-up' approach to bimetallic molecular clusters.

Reactions between ethylenediamine (en) solutions of the intermetallic Zintl phases K(3)E(7) (E = P, As) and a series of homoleptic post-transition metal organometallics such as Cu(5)(Mes)(5), M(C(6)H(5))(2) (M = Zn, Cd) and In(C(6)H(5))(3) have yielded a family of novel bimetallic cluster anions. These new species were isolated as [K(2, 2,2-crypt)](+) salts in [K(2,2,2-crypt)](4)Cu(2)E(14) (E = P (1), As (2)), [K(2,2,2-crypt)](4)ZnE(14) (E = P (3), As (4)), [K(2,2,2-crypt)](4)CdP(14) x 6py (5) and [K(2,2,2-crypt)](2)E(7)InPh(2) (E = P (6), As (7)). Species 2, 3, 5 and 6 were crystallographically characterised by single-crystal X-ray diffraction. The stability of all of the cluster anions in solution was confirmed by electrospray mass-spectrometry and by (1)H, (13)C{(1)H} and (31)P{(1)H} NMR spectroscopy when possible.