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2013-GermanCzerwinski-Shanghai TcVII PuVII

Lecture given at Shanghai

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2013-GermanCzerwinski-Shanghai TcVII PuVII

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  1. Heptavalent state of transuranium elements, technetium and other elements of the Periodic Table German K., Czerwinski K., Grigoriev M., Fedosseev A., Safonov A., Poineau F. , Maruk A., Peretrukhin V. A.N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS University of Nevada Las-Vegas 2013

  2. 2 The first publication on Np(VII) and Pu(VII) in 1967

  3. 3 V.F. Peretrukhin, G.T. Seaborg, N..N. Krot, LNL, Berkley, 1998

  4. 4 Periodic Table and heptavalent state of elements • Period is variable : 2, 8, 8, 18, 18, 32…? • Zones of implacability exist • For huge part - It works ! ! ! VII

  5. 5 Detailed fig In: Jarvinen et all Plutonium • Interatomic distances in metals/simple matter A.Wells “Struct.Inorg.Chem.” • Lost : P,S, Br, I, Po, At, Fr, Ra, Ac, Np, Pu, Am, Cm, Bk, Cf TRU

  6. 6 Synthesis and the types of An(VII) • Crystalline compounds of An(VII) can be prepared by deep oxidation of actinides in strongly alkaline conditions. • Both interaction of solid components and also conducting the oxidation in alkaline solutions. • Compounds of An(VII) are stable only in strong alkali, and rapidly decompose in neutral or acidic conditions. • An(VII) are quite variable in composition: formally they could be considered to contain anions AnO65-, AnO53-, [AnO4(OH)2]3-, [An2O8(OH)2]4- andAnO4- but the latter is not supported by X-ray analyses. • A short number of the solid compounds containing AnO65-, and AnO53- anions were isostructural to corresponding ortho- and meso- rhenates ReO65-, ReO53- (but no analogy in solutions).

  7. 7 MAnO4(·nH2O) (M – alkali metal) • It was estimated by N.N. Krot and the followers that the transuranium(VII) compounds like MAnO4(·nH2O) (M – alkali metal) have the structures similar to uranates(VI) of alkali earth metals. • They contain shortened linear groupsAnO23+ and O– bridges collecting all into anionic layers. Structural type of BaUO4. (Reis A.H. et al. JINC, 1976).

  8. 8 BaUO4 structural type compounds • Lattice parameters for different U(VI), Np(VI) (lit. data) and Np(VII) compounds (IPCE data) • 1 – U compounds • 2 – Np compounds • Chemical properties of Np(VI) and Np(VII) compounds are different • LiReO4*1.5H2O contra LiTcO4*3H2O

  9. 9 IR spectral data indicates Np-O and Np=O difference Evident splitting at the CsNpO4 spectrum indicates/supports the presence of two types of Np-O bonds: • O=Np=O • Np-O-Np In Li5NpO6all the Np-O bonds are of the same nature

  10. Mossbauer spectra of Np(VII) compounds • 1 – CsNpO4 • 2 – Na3NpO4(OH)2*nH2O • 3 – Li5NpO6 • 4 – frozen solution of Np(VII) in 10M NaOH • Dots - experiment, curve – squared plotting

  11. 11 In this way : Transuranic(VII) MAnO4(·nH2O) compounds are completely different : from MXO4xnH2O (X – elements of the 7th Group from Periodic Table, Mn, Tc, Re, n = 0, 1, 1.5, 3) from Tc(VII) acid German,Peretrukhin 2003 Poineau, German 2010 from Re(VII) acid Beyer H. et all. Angew. Chem., 1968 from I(VII) acid from Cl(VII) acid Структурный тип BaUO4. (Reis A.H. et al. JINC, 1976). (Maruk A.Ya. et al. Russ. Coord. Chem.2011) and from TcO3+ Pertechnetyl Fluorosulfate, [TcO3][SO3F] – ZAAC, 2007 J.Supeł, U. Abram et all. Berlin, Freie Universität.

  12. LiTcO4 · 6/2H2O6/2=3 Isostructural: LiBrO4·3H2O LiClO4 · 3H2O LiMnO4 · 3H2O LiReO4 · 1.5H2O LiReO4 · H2O - Analogous are absent More diffused 4d electrons in Re compared to 3d electrons in Tc

  13. Isostructural pertechnetate salts with cation : anion = 1:1 *Not determined . \ doesn’t exists –No similarity to Tc +Isostructural

  14. 12 Np(VII) & I(VII) Anionic chain [(Np2O8)(OH)2]n4n-in the structure of Li[Co(NH3)6][(Np2O8)(OH)2]·2H2O (Burns J., Baldwin W., Stokely J. Inorg. Chem., 1973). Neutral chains in HIO4. ( Smith, T. et all. Inorg.Chem., 1968) • Two types of Np in Np(VII) compound while only one I in I(VII) • One bridging O in Np(VII) while two bridging O in I(VII) • Np(VII) is stable in alkali while I(VII) – in acids

  15. 13 The first Pu(VII) single crystal

  16. 14

  17. 15 Na4[AnO4(OH)2](OH)∙2H2O Np1-O1 1.891(2) Pu1-O1 1.8824(15) Np1-O2 1.888(2) Pu1-O2 1.8805(18) Np1-O3 1.917(2) Pu1-O3 1.9109(15) Np1-O4 1.880(2)Pu1-O4 1.8811(19) Np1-O5 2.315(2) Pu1-O5 2.2952(19) Np1-O6 2.362(2)Pu1-O6 2.339(2) An-OH distances are more sensible to actinide contraction than An=O distances

  18. 16 Several mixed cation compounds of Np(VII) and Pu(VII) NaRb2[NpO4(OH)2]·4H2O (I): a = 8.2323(2), b = 13.4846(3), c = 9.9539(2) Å, β = 102.6161(12)°, sp. gr. P21/n, Z = 4, R1 [I > 2σ(I)] = 0.0179. NaRb2[NpO4(OH)2]·4H2O (II): a = 5.4558(2), b = 12.4478(3), c = 7.9251(2) Å, β = 103.6310(13)°, sp. gr. P21/n, Z = 2, R1 [I > 2σ(I)] = 0.0218. NaCs2[NpO4(OH)2]·4H2O (III): a = 15.0048(4), b = 9.1361(2), c = 10.6747(3) Å, β = 129.7361(9)°, sp. gr. C2/c, Z = 4, R1 [I > 2σ(I)] = 0.0148. NaRb5[PuO4(OH)2]2·6H2O (IV): a = 6.4571(1), b = 8.2960(1), c = 10.8404(2) Å, α = 105.528(1), β = 97.852(1), γ = 110.949(1)°, sp. gr. P-1, Z = 2, R1 [I > 2σ(I)] = 0.0189. NaRb2[PuO4(OH)2]·4H2O (V): a =8.2168(2), b = 13.4645(3), c = 9.9238(2) Ǻ, β = 102.6626(12)°, sp. gr. P21/n, Z = 4, R1 [I > 2σ(I)] = 0.0142. NaCs2[PuO4(OH)2]·4H2O (VI):a = 11.1137(2), b =9.9004(2), c = 10.5390(2) Ǻ, β = 101.0946(11)°, sp. gr. C2/c, Z = 4, R1 [I > 2σ(I)] = 0.0138. Anion of [PuO4(OH)2]3- in the structure of IV

  19. 17 Selected interatomic distances and torsion angles in the structures I – VI : III III IV V VI Bond(Å) An=O 1.8790(12)21.8690(9) 21.8884(9)1.8695(15)1.8685(12)21.8868(15) 1.8855(13) 21.9138(9)21.8944(9)1.8724(15)1.8761(12)21.8876(14) 1.8955(13) 1.8919(15) 1.8897(12) 1.9223(13)1.8985(16)1.9144(12) An-O(OH) 2.3259(13)22.3750(9)22.3643(9)2.3197(16)2.3083(13)22.3236(15) 2.3382(13)2.3556(15)2.3229(13) Angle (º)III III IV V VI H-O…O-H 145(4) 180133(4) 39(4)140(3)48(5)

  20. 18 Recently a new way for Np(VII) compound preparation was proposed by Fedosseev and co-workers [(2008)]: electrochemical oxidation in acetate solutions. The new compounds of МNpO4·nH2O type, where М – unicharged cation of alkali metal, ammonium, silver, guanidinium or tetraalkylammonium and Np(VII) with bicharged cations of alkaline earth metals,and also Cu, CdandZn. All these compounds have been thoroughly characterized by means of chemical analyses, IR and UV-vis spectroscopy. The study confirmed, that…

  21. 19 Pu(VII) compounds are close structural and chemical analogues of Np(VII) ones

  22. Tc(VII) & Pu(VII), Np(VII) Pu(VII) and Tc(VII) are different in (cry,ele)-structure, ligand arrangement, stability and chemical properties ! 1000 ppm

  23. 4 Periodic Table and heptavalent state of elements • Period is variable : 2, 8, 8, 18, 18, 32…? • Zones of implacability exist • For huge part - It works ! ! ! VII

  24. 20 An(VII) - Tc&Re(VII) • Structural and chemical data obtained in recent years by X-ray-s-c, IR and EXAFS investigations of the new compounds of • heptavalent neptunium and plutonium, • heptavalent technetium and rhenium • confirm the earlier prevailing opinion about the absence of a deep similarity in physico-chemical properties between the heptavalent transuranic elements and the elements of Group VII of the short form of the Periodic table and the formal nature of some of the structural similarities among the considered heptavalent compounds. • Principally one can attend the formation of Pu(VIII) but it is not the aqueous media that could stand its oxidizing power.

  25. BessonovPerminovKrot,GrigorievPeretrukhinGermanCzerwinskiPoineauBessonovPerminovKrot,GrigorievPeretrukhinGermanCzerwinskiPoineau Thank you for your Attention!

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