Reactions of the technetium(I) nitrosyl complex [Tc(NO)(Cp)(PPh(3))Cl] with triphenylphosphine chalcogenides EPPh(3) (E = O, S, Se), and Ag(PF(6)) in a CH(2)Cl(2)/MeOH mixture (v/v, 2/1) result in an exchange of the chlorido ligand and the formation of Tc(NO)(Cp)(PPh(3))(EPPh(3)) compounds. The cationic acetonitrile complex [Tc(NO)(Cp)(PPh(3))(NCCH(3))]^(+) is formed when the reaction is conducted in NCCH(3) without additional ligands. During the isolation of the corresponding …