The first examples of molecular telluride complexes, W6Te8L6 [L =pyridine (py), piperidine (pip), and PEt3], and the reduced salt [Na(py)(6)](+)[W6Te8(py)(6)](-) were discovered. The amine complexes were prepared by reaction of W6Cl12 With Na2Te or a Na2Te/Na2Te2 mixture in the amine solvents, whereas W6Te8(PEt3)6 was established by displacement of pyridine in W6Te8(py)(6) by PEt3. The cluster unit, W6Te8, showed characteristic T-1n W-Te stretching vibrations around 180-200 cm(-1). From XPS the W4f(7/2) binding energy of 30.8 eV for W6Te8L6 compared favorably with values of 30.5 and 30.8 eV for the sulfide and selenide analogues, respectively. Crystallographic data for the three compounds on which structure analyses were performed are as follows: W6Te8(pip)(6) . 6pip, hexagonal, R (3) over bar, a = 17.738(6) Angstrom, c = 24.318(10) Angstrom, Z = 3; W6Te8(PEt3)(6), monoclinic, C2/c, a = 24.724(6) Angstrom, b = 19.716(4) Angstrom, c = 13.543(9) Angstrom, beta = 108.56(3)degrees, Z = 4; [Na(py)(6)](+)[W6Te8(py)(6)](-). py, triclinic, P (1) over bar, a = 12.433(3) Angstrom, b = 12.760(2) Angstrom, c = 12.882(2) Angstrom, alpha = 96.78(1)degrees, beta = 100.03(1)degrees, gamma = 98.58(1)degrees, Z = 1. The average W-Te bond distance of 2.753 Angstrom is very close to the average W-W bond distance of 2.748 Angstrom in these telluride clusters. For the anionic complex, both the small distortion of the octahedral cluster unit and the shortening of the average W-W bond distance confirmed addition of the extra electron to a bonding orbital in the reduced 21e cluster unit. Extended Huckel MO calculations indicate that the structural distortion of the [W6Te8(py)(6)](-) anion arises from the Jahn-Teller effect on the E-2(g) ground state. The unique cationic unit [Na(py)(6)](+) is the first documented example of a sodium ion octahedrally coordinated with six pyridine molecules.