Reduction of TaCl5 with either Ga or Ga2Cl4, in the presence of NaCl, in a sealed borosilicate glass ampule at 500 degreesC, followed by aqueous Soxhlet extraction and treatment with SnCl2 and hydrochloric acid, yielded Ta-6(mu-Cl)(12)-Cl-2(OH2)(4).4H(2)O in 92% (Ga) or 96% (Ga2Cl4) yield. Ga2Cl4, a probable intermediate in the Ga-based reduction, is a more convenient reductant than Ga because it is readily dispersed in the reaction mixture, and these mixtures do not require homogenizations in order to afford high yields. Ta-6(mu-Cl)(12)Cl-2(OH2)(4).4H(2)O was converted by ligand exchange to the first tetraalkylammonium derivative, [N(CH2Ph)Bu-3](4)[Ta-6(mu-Cl)(12)Cl-6], of the reduced cluster core Ta-6(mu-Cl)(12)(2+), in 88% yield. [N(CH2Ph)Bu-3](4)[Ta-6(mu-Cl)(12)Cl-6] crystallizes from 1,2-dichloroethane/toluene mixtures in two crystalline morphologies, a nonsolvated cubic form and a solvated needle form. The solid-state molecular structures of both crystalline morphologies of [N(CH2Ph)Bu-3](4)[Ta-6(mu-Cl)(12)Cl-6] consist of octahedral, 16 VEC hexatantalum cluster anions with an average Ta-Ta distance of 2.900[2] Angstrom, a Ta-Cl(bridge) distance of 2.463[2] Angstrom, a Ta-Cl(terminal) distance of 2.567[5] Angstrom, and a Ta-Cl-Ta angle of 72.1[1]degrees for the cubic form, and for the solvated needle morphology, an average Ta-Ta distance of 2.900[1] Angstrom, a Ta-Cl(bridge) distance of 2.461[1]Angstrom, a Ta-Cl(terminal) distance of 2.567[3] Angstrom, and a Ta-Cl-Ta angle of 72.19[7]degrees.