2 + 1 Tricarbonyl Complexes of Technetium(I) with a Combination of N,N‑Bidentate Ligands and Ethyl Isocyanoacetate: How Strong Is the Interfering Effect of Chloride Ions on Their Formation?

Technetium­(I) 2 + 1 tricarbonyl complexes with a combination of N,N-bidentate ligands (2,2′-bipyridine, bipy; 1,10-phenanthroline, phen) and ethyl isocyanoacetate were prepared and characterized by NMR, IR, UV/visible, and luminescence spectroscopies and by high-performance liquid chromatography (HPLC). The crystal structures of [99Tc­(CO)3(bipy)­(CNCH2COOEt)]­(ClO4) (in the form of a solvate with 0.5CH2Cl2) and [99Tc­(CO)3(phen)­(CNCH2COOEt)]­(ClO4) (in the form of an adduct with an outer-sphere phen molecule) were determined by single-crystal X-ray diffraction. To evaluate the interfering effect of chloride ions on the formation of the 2 + 1 complexes, the kinetics of the replacement of labile monodentate ligand X in the complexes [MX­(CO)3(N∧N)] (M = Re, 99Tc; N∧N = bipy, phen; X = Cl–, ClO4 –) by CNCH2COOEt in ethanol were compared. The 99Tc bipy complexes with X = ClO4 – (according to the IR data, perchlorate anion in ethanol is displaced from the coordination sphere by the solvent molecule) and X = Cl– are characterized by close ligand replacement rates. In the case of the 99Tc complexes with phen and Re complexes with both phen and bipy, the chloride complexes are appreciably less reactive than the chloride-free complexes. The technetium complexes are considerably more reactive in ligand replacement than their rhenium analogues. In the chloride-containing medium (saline), the complex [99mTc­(CO)3(bipy)­(CNCH2COOEt)]+ can be prepared under the conditions acceptable for nuclear medical applications, although higher isonitrile concentrations are required as compared to the chloride-free system.