Synthesis, characterization and reactions of [Tc(NS)X4]− complexes (XCl, Br, NCS)

Tetrafluoridonitridotechnetate(VI) – Reactions and Structures

“…The chemistry of nitrido complexes of technetium(VI) has been extensively studied and the formation of [TcN X 4 ] – or [TcN X 5 ] 2– ( X = Cl, Br) anions as key compounds of this chemistry from various reactions is well established . The structures of the tetraphenylarsonium and tetrabutylammonium salts of [TcNCl 4 ] – and [TcNBr 4 ] – as well as those of Cs 2 [TcNCl 5 ], Cs 2 [TcNBr 5 ] and (NEt 4 )[TcNBr 4 (H 2 O)] have been determined by X‐ray diffraction , , …”

[TcCl4(H2O)2] and [Cl3(H2O)2TcOTc(H2O)2Cl3]– two molecular intermediates of the hydrolysis of technetium(iv)

“…[1][2][3][4][5] Indeed, to the best of our knowledge only one crystallographically characterised technetium(IV) aqua complex exists, the [TcCl 5 (H 2 O)] 2 anion, which crystallizes together with an oxonium ion and two molecules of 15-crown-5. 6 Treatment of technetium(IV) tetrachloride, TcCl 4 , with water immediately yields insoluble TcO 2 , a black-brown, amorphous solid, which contains an undefined amount of water. Thermodynamic model calculations suggest that this hydrolysis proceeds even at pH , 1.…”

Tetrahydrothiophene complexes of technetium(IV)

“…Although the binary chloride TcCl 4 , which is built of polymeric chains consisting of edge-sharing {TcCl 6 } octahedra, has been shown to be more reactive than the corresponding hexachlorotechnetate(IV) anion and seems to be a promising starting compound [2], the difficulty of its preparation prevents a broader application.…”

“…2 [12]. It is evident, that the thioether ligand is only weakly bonded and the Tc-S bond has approximately the same length as in [TcCl 4 (tht) 2 ]. The small differences may be explained by the structural trans-influence of the ligands.…”