The
attachment of an ethyne substituent in the para position of
phenylisocyanide, CNPhpCCH, 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(CNPhazole)6]+ cation. The free, uncoordinated “Click”
product is obtained from a reaction of the corresponding tetrakis(CNPhazole)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(CNPhazole)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(CNPhazole)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.