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Technetium compounds

Technetium compounds are chemical compounds containing the chemical element technetium. Technetium can form multiple oxidation states, but often forms in the +4 and +7 oxidation states. Because technetium is radioactive, technetium compounds are extremely rare on Earth.

Pertechnetate and derivatives

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Main article: Pertechnetate
 
Pertechnetate is one of the most available forms of technetium. It is structurally related to permanganate.

The most prevalent form of technetium that is easily accessible is sodium pertechnetate, Na[TcO4]. The majority of this material is produced by radioactive decay from [99MoO4]2−:[1][2]

[99MoO4]2− → [99mTcO4]− + e−

Pertechnetate (tetroxidotechnetate) TcO−
4 behaves analogously to perchlorate, both of which are tetrahedral. Unlike permanganate (MnO−
4), it is only a weak oxidizing agent.

Related to pertechnetate is technetium heptoxide. This pale-yellow, volatile solid is produced by oxidation of Tc metal and related precursors:

4 Tc + 7 O2 → 2 Tc2O7

It is a molecular metal oxide, analogous to manganese heptoxide. It adopts a centrosymmetric structure with two types of Tc−O bonds with 167 and 184 pm bond lengths.[3]

Technetium heptoxide hydrolyzes to pertechnetate and pertechnetic acid, depending on the pH:[4][5]

Tc2O7 + 2 OH− → 2 TcO4− + H2O
Tc2O7 + H2O → 2 HTcO4

HTcO4 is a strong acid. In concentrated sulfuric acid, [TcO4]− converts to the octahedral form TcO3(OH)(H2O)2, the conjugate base of the hypothetical triaquo complex [TcO3(H2O)3]+.[6]

Other chalcogenide derivatives

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Technetium forms a dioxide,[7] disulfide, diselenide, and ditelluride. An ill-defined Tc2S7 forms upon treating pertechnetate with hydrogen sulfide. It thermally decomposes into disulfide and elemental sulfur.[8] Similarly the dioxide can be produced by reduction of the Tc2O7.

Unlike the case for rhenium, a trioxide has not been isolated for technetium. However, TcO3 has been identified in the gas phase using mass spectrometry.[9]

Simple hydride and halide complexes

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Technetium forms the simple complex TcH2−
9. The potassium salt is isostructural with ReH2−
9.[10]

 
TcCl4 forms chain-like structures, similar to the behavior of several other metal tetrachlorides.

The following binary (containing only two elements) technetium halides are known: TcF6, TcF5, TcCl4, TcBr4, TcBr3, α-TcCl3, β-TcCl3, TcI3, α-TcCl2, and β-TcCl2. The oxidation states range from Tc(VI) to Tc(II). Technetium halides exhibit different structure types, such as molecular octahedral complexes, extended chains, layered sheets, and metal clusters arranged in a three-dimensional network.[11][12] These compounds are produced by combining the metal and halogen or by less direct reactions.

TcCl4 is obtained by chlorination of Tc metal or Tc2O7 Upon heating, TcCl4 gives the corresponding Tc(III) and Tc(II) chlorides.[12]

TcCl4 → α-TcCl3 + 1/2 Cl2
TcCl3 → β-TcCl2 + 1/2 Cl2

The structure of TcCl4 is composed of infinite zigzag chains of edge-sharing TcCl6 octahedra. It is isomorphous to transition metal tetrachlorides of zirconium, hafnium, and platinum.[12]

 
Chloro-containing coordination complexes of technetium (99Tc) in various oxidation states: Tc(III), Tc(IV), Tc(V), and Tc(VI) represented.

Two polymorphs of technetium trichloride exist, α- and β-TcCl3. The α polymorph is also denoted as Tc3Cl9. It adopts a confacial bioctahedral structure.[13] It is prepared by treating the chloro-acetate Tc2(O2CCH3)4Cl2 with HCl. Like Re3Cl9, the structure of the α-polymorph consists of triangles with short M-M distances. β-TcCl3 features octahedral Tc centers, which are organized in pairs, as seen also for molybdenum trichloride. TcBr3 does not adopt the structure of either trichloride phase. Instead it has the structure of molybdenum tribromide, consisting of chains of confacial octahedra with alternating short and long Tc—Tc contacts. TcI3 has the same structure as the high temperature phase of TiI3, featuring chains of confacial octahedra with equal Tc—Tc contacts.[12]

Several anionic technetium halides are known. The binary tetrahalides can be converted to the hexahalides [TcX6]2− (X = F, Cl, Br, I), which adopt octahedral molecular geometry.[14] More reduced halides form anionic clusters with Tc–Tc bonds. The situation is similar for the related elements of Mo, W, Re. These clusters have the nuclearity Tc4, Tc6, Tc8, and Tc13. The more stable Tc6 and Tc8 clusters have prism shapes where vertical pairs of Tc atoms are connected by triple bonds and the planar atoms by single bonds. Every technetium atom makes six bonds, and the remaining valence electrons can be saturated by one axial and two bridging ligand halogen atoms such as chlorine or bromine.[15]

Simple carbide complexes

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Technetium forms the simple carbon insertion phases with low carbon content up to 17 at.% of C when reacted with grphite[16] or by thermolisys of organic pertechnetates.[17] Tc is considered to be the last d-element to have some low but notable affinity to carbon. [18]

Coordination and organometallic complexes

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[[Technetium (99mTc) sestamibi]] ("Cardiolite") is widely used for imaging of the heart.

Technetium forms a variety of coordination complexes with organic ligands. Many have been well-investigated because of their relevance to nuclear medicine.[19]

Technetium forms a variety of compounds with Tc–C bonds, i.e. organotechnetium complexes. Prominent members of this class are complexes with CO, arene, and cyclopentadienyl ligands.[20] The binary carbonyl Tc2(CO)10 is a white volatile solid.[21] In this molecule, two technetium atoms are bound to each other; each atom is surrounded by octahedra of five carbonyl ligands. The bond length between technetium atoms, 303 pm,[22][23] is significantly larger than the distance between two atoms in metallic technetium (272 pm). Similar carbonyls are formed by technetium's congeners, manganese and rhenium.[24] Interest in organotechnetium compounds has also been motivated by applications in nuclear medicine.[20] Technetium also forms aquo-carbonyl complexes, one prominent complex being [Tc(CO)3(H2O)3]+, which are unusual compared to other metal carbonyls.[20]

See also

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References

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  1. ^ Schwochau 2000, pp. 127–136.
  2. ^ Moore, P. W. (April 1984). "Technetium-99 in generator systems" (PDF). Journal of Nuclear Medicine. 25 (4): 499–502. PMID 6100549. Retrieved 2012-05-11.
  3. ^ Krebs, B. (1969). "Technetium(VII)-oxid: Ein Übergangsmetalloxid mit Molekülstruktur im festen Zustand (Technetium(VII) Oxide, a Transition Metal Oxide with a Molecular Structure in the Solid State)". Angewandte Chemie. 81 (9): 328–329. doi:10.1002/ange.19690810905.
  4. ^ Schwochau 2000, p. 127.
  5. ^ Herrell, A. Y.; Busey, R. H.; Gayer, K. H. (1977). Technetium(VII) Oxide, in Inorganic Syntheses. Vol. XVII. pp. 155–158. ISBN 978-0-07-044327-3.
  6. ^ Poineau F; Weck PF; German K; Maruk A; Kirakosyan G; Lukens W; Rego DB; et al. (2010). "Speciation of heptavalent technetium in sulfuric acid: structural and spectroscopic studies" (PDF). Dalton Transactions. 39 (37): 8616–8619. doi:10.1039/C0DT00695E. PMID 20730190. S2CID 9419843.
  7. ^ Schwochau 2000, p. 108.
  8. ^ Schwochau 2000, pp. 112–113.
  9. ^ Gibson, John K. (1993). "High-Temperature Oxide and Hydroxide Vapor Species of Technetium". Radiochimica Acta. 60 (2–3): 121–126. doi:10.1524/ract.1993.60.23.121. S2CID 99795348.
  10. ^ Schwochau 2000, p. 146.
  11. ^ Johnstone, E. V. (May 2014). Binary Technetium Halides (Thesis). University of Nevada, Las Vegas. doi:10.34917/5836118 – via UNLV Theses, Dissertations, Professional Papers, and Capstones.
  12. ^ a b c d Poineau, Frederic; Johnstone, Erik V.; Czerwinski, Kenneth R.; Sattelberger, Alfred P. (2014). "Recent Advances in Technetium Halide Chemistry". Accounts of Chemical Research. 47 (2): 624–632. doi:10.1021/ar400225b. PMID 24393028.
  13. ^ Poineau, Frederic; Johnstone, Erik V.; Weck, Philippe F.; Kim, Eunja; Forster, Paul M.; Scott, Brian L.; Sattelberger, Alfred P.; Czerwinski, Kenneth R. (2010). "Synthesis and Structure of Technetium Trichloride". Journal of the American Chemical Society. 132 (45): 15864–5. doi:10.1021/ja105730e. PMID 20977207.
  14. ^ Schwochau, K. (2000). Technetium: Chemistry and Radiopharmaceutical Applications. Weinheim, Germany: Wiley-VCH. ISBN 978-3-527-29496-1.
  15. ^ German, K. E.; Kryutchkov, S. V. (2002). "Polynuclear Technetium Halide Clusters". Russian Journal of Inorganic Chemistry. 47 (4): 578–583. Archived from the original on 2015-12-22.
  16. ^ German, K. E.; Peretrukhin, V. F.; Gedgovd, K. N.; Grigoriev, M. S.; Tarasov, A. V.; Plekhanov, Yu V.; Maslennikov, A. G.; Bulatov, G. S.; Tarasov, V. P.; Lecomte, M. (2005). "Tc Carbide and New Orthorhombic Tc Metal Phase". Journal of Nuclear and Radiochemical Sciences. 6 (3): 211–214. doi:10.14494/jnrs2000.6.3_211.
  17. ^ Kuznetsov, Vitaly V.; German, Konstantin E.; Nagovitsyna, Olga A.; Filatova, Elena A.; Volkov, Mikhail A.; Sitanskaia, Anastasiia V.; Pshenichkina, Tatiana V. (2023-10-31). "Route to Stabilization of Nanotechnetium in an Amorphous Carbon Matrix: Preparative Methods, XAFS Evidence, and Electrochemical Studies". Inorganic Chemistry. doi:10.1021/acs.inorgchem.3c03001. ISSN 0020-1669.
  18. ^ Wang, Qinggao; German, Konstantin E.; Oganov, Artem R.; Dong, Huafeng; Feya, Oleg D.; Zubavichus, Ya V.; Murzin, V. Yu (2016-02-08). "Explaining stability of transition metal carbides – and why TcC does not exist". RSC Advances. 6 (20): 16197–16202. doi:10.1039/C5RA24656C. ISSN 2046-2069.
  19. ^ Bartholomä, Mark D.; Louie, Anika S.; Valliant, John F.; Zubieta, Jon (2010). "Technetium and Gallium Derived Radiopharmaceuticals: Comparing and Contrasting the Chemistry of Two Important Radiometals for the Molecular Imaging Era". Chemical Reviews. 110 (5): 2903–20. doi:10.1021/cr1000755. PMID 20415476.
  20. ^ a b c Alberto, Roger (2010). "Organometallic Radiopharmaceuticals". Medicinal Organometallic Chemistry. Topics in Organometallic Chemistry. Vol. 32. pp. 219–246. doi:10.1007/978-3-642-13185-1_9. ISBN 978-3-642-13184-4.
  21. ^ Hileman, J. C.; Huggins, D. K.; Kaesz, H. D. (1961). "Technetium carbonyl". Journal of the American Chemical Society. 83 (13): 2953–2954. doi:10.1021/ja01474a038.
  22. ^ Bailey, M. F.; Dahl, Lawrence F. (1965). "The Crystal Structure of Ditechnetium Decacarbonyl". Inorganic Chemistry. 4 (8): 1140–1145. doi:10.1021/ic50030a011.
  23. ^ Wallach, D. (1962). "Unit cell and space group of technetium carbonyl, Tc2(CO)10". Acta Crystallographica. 15 (10): 1058. doi:10.1107/S0365110X62002789.
  24. ^ Schwochau 2000, pp. 286, 328.
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