The synthesis and characterization of a cationic technetium nitrosyl complex: The X-ray crystal structure of [TcCl(NO)(DPPE)2](PF6) · CH2Cl2

The reaction of the ammonium pertechnetate with a stochiometric excess of hydroxylamine hydrochloride in methanol yields a nitrosyl containing intermediate which can subsequently be reacted with reducing ligands to form nitrosyl complexes in various oxidation states. The reaction with a sixfold excess of diphenyl-phosphinoethane (DPPE) yields the Tc(I) cation [TcCl(NO)(DPPE)2]+ which can be precipitated cleanly with tetraphenylborate. The infrared spectrum displays an absorption at 1728 cm−1 which corresponds to the nitrosyl group. The ESI(+) mass spectrum displays the parent ion [TcCl(NO)(DPPE)2]+ as the only signal at 960 m/z. The X-ray crystal structure of the hexafluorophosphate salt shows a mutually trans arrangement of the nitrosyl and chloride ligands with the two bidentate phosphine ligands coordinated in the equatorial plane. The nitrosyl and chloride ligands display the usual site disorder which makes discussion of bond lengths tenuous. However, the Tc–N–O bond angle of 179.0(2)° reflects the sp hybridization of the nitrosyl nitrogen atom. The Tc–P bonds are somewhat elongated at 2.3810(6), 2.3947(6), 2.4096(5) and 2.4321(6) Å, due to the steric congestion around the metal ion. The Tc–Cl bond is unexceptional at 2.3262(7) Å. The coordination geometry of this complex is best described as a distorted octahedron.