The reduction of ammonium pertechnetate with bis(diphenylphosphino)methane (dppm), and with diphenyl-2-pyridyl phosphine (Ph(2)Ppy), has been investigated. The neutral Tc(II) complex, trans-TcCl2(dppm)(2) (1), has been isolated from the reaction of (NH4)[TcO4] with excess dppm in refluxing EtOH/HCl. Chemical oxidation with ferricinium hexafluorophosphate results in formation of the cationic Tc(III) analogue, trans-[TcCl2(dppm)(2)](PF6) (2). The dppm ligands adopt the chelating bonding mode in both complexes, resulting in strained four member metallocycles. With excess PhPpy, the reduction of (NH4)[TcO4] in refluxing EtOH/HCI yields a complex with one chelating Ph-2-Ppy ligand and one unidentate Ph(2)Ppy ligand, mer-TcCl3(Ph(2)Ppy-P,N)(Ph(2)Ppy-P) (3). The cationic Tc(III) complexes, trans-[TcCl2(Ph2P(O)py-N,O)(2)](PF6) (4) and trans-[TcCl2(dppmO-P,O)(2)](PF6) (5) (Ph2P(O)py = diphenyl-2-pyridyl phosphine monoxide and dppmO = bis(diphenylphosphino)methane monoxide), have been isolated as byproducts from the reactions of (NH4)[TcO4] with the corresponding phosphine. The products have been characterized in the solid state and in solution via a combination of single-crystal X-ray crystallography and spectroscopic techniques. The solution state spectroscopic results are consistent with the retention of the bonding modes revealed in the crystal structures.