Technetium Complexes with an Isocyano-alkyne Ligand and Its Reaction Products

The attachment of an ethyne substituent in the para position of phenylisocyanide, CNPh^pC≡CH, enables the isocyanide to replace carbonyl ligands in the coordination sphere of common technetium(I) starting materials such as (NBu₄)[Tc₂(μ-Cl)₃(CO)₆]. The ligand exchange proceeds under thermal conditions and finally forms the corresponding hexakis(isocyanide)technetium(I) complex. The product undergoes a copper-catalyzed cycloaddition ("Click" reaction), e.g., with benzyl azide, which gives the [Tc(CNPh^azole)₆]⁺ cation. The free, uncoordinated "Click" product is obtained from a reaction of the corresponding tetrakis(CNPh^azole)copper(I) complex and NaCN. It readily reacts with mer-[Tc(CO)₃(tht)(PPh₃)₂](BF₄) (tht = tetrahydrothiophene) under exchange of the thioether ligand. Alternatively, [Cu(CNPh^azole)₄]⁺ can be used as a transmetalation reagent for the synthesis of the hexakis(isocyanide)technetium(I) complex, which is the preferable approach for the synthesis of the technetium complex with the short-lived nuclear isomer ^99mTc, and a corresponding protocol for [^99mTc(CNPh^azole)₆]⁺ is reported. The ⁹⁹Tc and copper complexes have been studied by single-crystal X-ray diffraction and/or spectroscopic methods including IR and multinuclear NMR spectroscopy.