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Reactivity of uranium(iii) with H2E (E = S, Se, Te): synthesis of a series of mononuclear and dinuclear uranium(iv) hydrochalcogenido complexes.

ABSTRACT: We report the syntheses, electronic properties, and molecular structures of a series of mono- and dinuclear uranium(iv) hydrochalcogenido complexes supported by the sterically demanding but very flexible, single N-anchored tris(aryloxide) ligand (AdArO)3N)3-. The mononuclear complexes [((AdArO)3N)U(DME)(EH)] (E = S, Se, Te) can be obtained from the reaction of the uranium(iii) starting material [((AdArO)3N)UIII(DME)] in DME via reduction of H2E and the elimination of 0.5 equivalents of H2. The dinuclear complexes [{((AdArO)3N)U}2(?-EH)2] can be obtained by dissolving their mononuclear counterparts in non-coordinating solvents such as benzene. In order to facilitate the work with the highly toxic gases, we created concentrated THF solutions that can be handled using simple glovebox techniques and can be stored at -35 °C for several weeks.

SUBMITTER: Franke SM

PROVIDER: S-EPMC5811169 | biostudies-other | 2015 Jan

REPOSITORIES: biostudies-other

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Reactivity of uranium(iii) with H2E (E = S, Se, Te): synthesis of a series of mononuclear and dinuclear uranium(iv) hydrochalcogenido complexes.

Franke Sebastian M SM Rosenzweig Michael W MW Heinemann Frank W FW Meyer Karsten K

Chemical science 20140929 1

We report the syntheses, electronic properties, and molecular structures of a series of mono- and dinuclear uranium(iv) hydrochalcogenido complexes supported by the sterically demanding but very flexible, single N-anchored tris(aryloxide) ligand (AdArO)3N)3-. The mononuclear complexes [((AdArO)3N)U(DME)(EH)] (E = S, Se, Te) can be obtained from the reaction of the uranium(iii) starting material [((AdArO)3N)UIII</su ...[more]

PMID: 29560170

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Project description:BackgroundSelenium and Tellurium have many common chemical properties as both belong to group 16 of the periodic table. High toxicities of Se and Te oxyanions cause environmental problems in contaminated soils and waters. Three strains (C4, C6 and C7) of selenite reducing and nanoparticle forming aerobic bacteria which were isolated from agricultural soils of India containing high concentrations of Se were investigated after 3.5 months of freeze-storage for their resistance against the toxic oxyanion tellurite and its reduction to non toxic elemental form Te(0) as well as nanoparticles formation.ResultsStrains C4, C6 and C7 reduced tellurite at maximum reduction rates of 2.3, 1.5 and 2.1 mg Te (IV)/L/d, respectively and produced extracellular Te(0) nanospheres as revealed from SEM-EDX analysis. Production of extracellular Te nanospheres has been described seldom. Further, concurrent reduction of both selenite and tellurite by bacteria was examined as these toxic oxyanions are often present together in natural environments, mine tailings or wastewater from copper refining. Interestingly, bioreduction of 100 mg/L selenite in shake flasks was not much affected by the presence of 10 mg/L tellurite but tellurite reduction rate increased 13 fold with selenite in the medium. The concurrent reduction of these oxyanions resulted in rarely described bioformation of extracellular nanoparticles composed of both Se and Te, reported first time for aerobically growing heterotrophic non-halophilic bacterial cultures. Duganella violacienigra, the closely related strain to C4 was also found to be resistant to oxyanions of Se and Te.ConclusionsSelenite reducing heterotrophic non-halophilic aerobic bacteria revived from 3.5 months freeze storage could successfully reduce toxic tellurite to non toxic elemental form and produced extracellular nanospheres during detoxification. Presence of relatively less toxic selenite in the medium triggers bioreduction of more toxic tellurite leading to formation of extracellular SeTe nanospheres which are sought by solar and optical recording media industry because of their excellent photovoltaic and optical properties. The bacterial cultures investigated in this study could be exploited commercially to remediate not only selenite and tellurite-contaminated soil and water but also for green synthesis of extracellular Se, Te and Se + Te nanospheres.

Dataset Information

Reactivity of uranium(iii) with H2E (E = S, Se, Te): synthesis of a series of mononuclear and dinuclear uranium(iv) hydrochalcogenido complexes.

Publications

Reactivity of uranium(iii) with H<sub>2</sub>E (E = S, Se, Te): synthesis of a series of mononuclear and dinuclear uranium(iv) hydrochalcogenido complexes.

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