Technetium Dichloride: A New Binary Halide Containing Metal–Metal Multiple Bonds

Abstract

Technetium dichloride has been discovered. It was synthesized from the elements and characterized by several physical techniques, including single crystal X-ray diffraction. In the solid state, technetium dichloride exhibits a new structure type consisting of infinite chains of face sharing [Tc(2)Cl(8)] rectangular prisms that are packed in a commensurate supercell. The metal-metal separation in the prisms is 2.127(2) Å, a distance consistent with the presence of a Tc≡Tc triple bond that is also supported by electronic structure calculations.

Synthesis and Characterization of Non‐Aqueous [TcXM‐PW11O39]n– with M = O, N: Comparing TcV and TcVI in Metal Oxide Matrices

“…The edge appears typically at a higher energy as the oxidation state is increased. This can however be complicated by the effects of covalency, which can shift the observed edge energy from what one would predict from oxidation state alone …”

Development of Alternative Technetium Waste Forms

“…The project evaluated a range of Tc containing alloys 1,2 , salts 3, and binary compounds 4,5,6,7 as potential waste forms. The results were published in the literature and as a Ph.D. thesis8.…”

Hydrothermal synthesis and solid-state structures of polynuclear technetium iodide compounds

“…[3] As part of an effort to expand our knowledge of technetium metal-metal bond chemistry, we prepared seven new binary halides (TcBr 4 , TcBr 3 , -TcCl 3 , -TcCl 2, and TcI 3 ). [4][5][6][7][8][9][10] The oxidation state of the Tc atom likely determines the extent to which Tc-Tc bonding occurs. In the tetrahalide TcBr 4 , there is no discernable metal-metal interaction.…”

“…Two main routes have proven fruitful for the synthesis of technetium binary halides: reaction between the elements in a sealed evacuated tube, [5,6] and reaction between Tc 2 (O 2 CCH 3 ) 4 Cl 2 and flowing HX gas (X = Cl, Br, I) at elevated temperatures. Technetium trihalides (TcBr 3 , TcI 3 and -TcCl 3 ) have been obtained from the reaction of Tc 2 (O 2 CCH 3 ) 4 Cl 2 with HX gas at 300 ºC.…”