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Access to pseudotetrahedral [Tc(NO)(Cp)(PPh 3 )X] 0,+ complexes (X = halide, Ph, CO) has been found by a convenient procedure starting from [Tc(NO)Y 2 (PPh 3 ) 2 (MeCN)] (Y = Cl, Br) and subsequent ligand exchange reactions.

{Tc(NO)(Cp)(PPh3)}+– a novel technetium(i) core

{Tc(NO)(Cp)(PPh₃)}⁺– a novel technetium(i) core