Several tellurometalates of the general formula [MTe(7)](n-) (n = 2, 3) have been isolated as salts of organic cations by reaction of suitable metal sources with polytelluride solutions in DMF. The [HgTe7](2-) anion has the same structure in both the NEt(4+) and the PPh(4)(+) salts except for a minor change in the ligand conformation. The [AgTe7](3-) and [HgTe7](2-) anions contain metal atoms coordinated in trigonal-planar fashion to eta(3)-Te-7(4-) ligands. The central Te atom of an eta(3)-Te-7(4-) ligand is coordinated to the metal atom and to two Te atoms in a "T"-shaped geometry consistent with a hypervalent 10 e(-) center. The planar [AuTe7](3-) anion may best be described as possessing a square-planar Au-III atom coordinated to an eta(3)-Te-5(4-) ligand and to an eta(1)-Te-2(2-) ligand. The reaction of [NEt(4)](n)[MTe(7)] (M = Hg, n = 2; M = Au, n = 3) with the activated acetylene dimethyl acetylenedicarboxylate (DMAD) has yielded the products [NEt(4)](n)[M(Te2C2(COOCH3)(2))(2)] (M = Hg, n = 2; M = Au, n = 1). The metal atoms are coordinated to two Te(COOCH3)C = C(COOCH3Te2- ligands, for M = Hg in a distorted tetrahedral fashion and for M = Au in a square-planar fashion.