ABSTRACT
Technetium pentacarbonyl fluoride [TcF(CO)5] was prepared for the first time by reaction of [TcI(CO)5] with solid AgF in a dichloromethane solution at -23 °C. Low temperature crystallization of the resulting compound in a glass vial yielded an unusual complex [Tc(CO)3(OH)0.49F0.51]4·[Tc(CO)5(BF4)] characterized by single crystal XRD.
ABSTRACT
Technetium(I) tetracarbonyl complexes with diethyldithiocarbamate and methylxanthate ligands [TcL(CO)(4)] (L = S(2)CNEt(2) and S(2)COMe) were prepared. Conditions required for the formation of these complexes were found. The crystal and molecular structure of the xanthate complex was determined by single-crystal X-ray diffraction. [Tc(S(2)CNEt(2))(CO)(4)] undergoes decarbonylation both in solution and in the course of vacuum sublimation with the formation of a dimer [Tc(S(2)CNEt(2))(CO)(3)](2) whose structure was determined by single-crystal X-ray diffraction. In donor solvents, [Tc(S(2)CNEt(2))(CO)(4)] and [Tc(S(2)COMe)(CO)(4)] undergo decarbonylation with the formation of tricarbonyl solvates [TcL(CO)(3)(Sol)]. The crystal structure of the pyridine solvate [Tc(S(2)CNEt(2))(CO)(3)(py)], chosen as an example, was determined by single-crystal X-ray diffraction. The possibility of using bidentate S-donor acidic ligands for tethering the tetracarbonyltechnetium fragment to biomolecules was examined.
Subject(s)
Organotechnetium Compounds/chemistry , Radiopharmaceuticals/chemistry , Thiocarbamates/chemistry , Crystallography, X-Ray , Ligands , Models, Molecular , Organotechnetium Compounds/chemical synthesis , Radiopharmaceuticals/chemical synthesis , Thiocarbamates/chemical synthesis , Xanthines/chemical synthesis , Xanthines/chemistryABSTRACT
The title compound, [Tc(CO)(6)]ClO(4), was synthesized by the reaction of [TcCl(CO)(5)] with AgClO(4), followed by acidification with HClO(4) under a CO atmosphere. The [Tc(CO)(6)](+) cation has close to idealized octa-hedral geometry, with the bond angles between cis-CO groups close to 90° and the Tc-C bond lengths in the range 2.025â (3)-2.029â (3)Å. The perchlorate anion is disordered over two crystallographically equivalent half-occupied positions. The Tc atom in the [Tc(CO)(6)](+) cation is located on an inversion centre.
