Some new low-valent, cationic complexes of technetium-99 have been prepared. Oxidation of Tc2(CO)10 (1) with NOPF6 in acetonitrile gave [Tc(CH3CN)(CO)5]PF6 (2) quantitatively. This complex constitutes a useful precursor for cationic carbonyl complexes, as exemplified by a variety of reactions with bi- and tridentate ligands from which air-stable, water-soluble complexes of type [LTc(CO)3]+(L = 1,4