Technetium(I) Carbonyl Dithiocarbamates and Xanthates

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.

Speciation and Oxidative Stability of Alkaline Soluble, Non-Pertechnetate Technetium

“…However, only one approach was examined this fiscal year. The approach is one described by Miroslavov and co-workers (see Miroslavov et al 2011, Miroslavov et al 2008, Sidorenko et al 2005, and Suglobov et al 2005 for recent leading references).…”

Synthesis of [99Tc(CO)6]+ Cation under Ambient Conditions

“…All the syntheses were performed at high CO pressures, [4][5][6][7][8] which does not comply with the modern safety requirements adopted in the majority of developed countries. Recently we reported the atmospheric-pressure synthesis of [ 99 TcHal(CO) 5 ], [9] which makes a wide range of higher technetium carbonyls synthetically accessible without using high CO pressures (subsequent transformations of [ 99 TcHal(CO) 5 ] into diverse tetra-and pentacarbonyl complexes are performed at ambient pressure [10][11][12][13] ). At the same time, preparation of the highest technetium carbonyl [ 99 Tc(CO) 6 ] + still required a high pressure of carbon monoxide.…”

Reactivity of the [M(PS)2]+ Building Block (M = ReIII and 99mTcIII; PS = Phosphinothiolate) toward Isopropylxanthate and Pyridine-2-thiolate

“…Xanthates and pyridine-2-thiolate derivatives are known bidentate ligands that have been coordinated to several metal ions, including rhenium and technetium. , Their structures allow delocalization of π electrons between the two donor atoms, as in dithiocarbamates (Scheme ).…”