A method for the preparation of eta(5)-metallocarborane complexes of technetium-99m in water was developed. The key to the procedure is the use of aqueous sodium or potassium fluoride, which prevents premature degradation of the Tc(I) starting material used to prepare the carborane complexes. Solid-phase extraction was used to purify Tc-metallocarboranes derived from both ortho and meta isomers, which were isolated in good to excellent yields in high radiochemical purities. In conjunction with these studies, a series of fluoride-based "kits" were developed to produce the key precursor [Tc-99m(CO)(3)(H2O)(3)](+) in the absence of any other stabilizing ligand. Using this approach, [Tc-99m(CO)(3)(H2O)(3)](+) could be prepared directly from (TcO4-)-Tc-99m under a range of pH values, including neutral pH, which affords the opportunity to develop one-pot labeling procedures for base-sensitive targeting vectors.