Cation-Cation Complexes of Pentavalent Uranyl: From Disproportionation Intermediates to Stable Clusters

被引:68
作者
Mougel, Victor [1 ]
Horeglad, Pawel [1 ]
Nocton, Gregory [1 ]
Pecaut, Jacques [1 ]
Mazzanti, Marinella [1 ]
机构
[1] CEA Grenoble, INAC, SCIB, Lab Reconnaissance Ion & Chim Coordinat, F-38054 Grenoble 09, France
关键词
actinides; cluster compounds; disproportionation; Schiff bases; uranium; MOLECULAR-STRUCTURE; URANIUM BIOREDUCTION; MAGNETIC-PROPERTIES; AQUEOUS-SOLUTION; COORDINATION; REDUCTION; CHEMISTRY; CRYSTAL; SPECTROSCOPY; REACTIVITY;
D O I
10.1002/chem.201001929
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Three new cation cation complexes of pentavalent uranyl, stable with respect to the disproportionation reaction, have been prepared from the reaction of the precursor [(UO(2)py(5))-(KI(2)py(2))](n) (1) with the Schiff base ligands salen(2-), acacen(2-), and salophen(2-) (H(2)salen = N,N'-ethylene-bis(salicylideneimine), H(2)acacen=-N,N'-ethylenebis(acetylacetoneimine), H(2)salophen=N,N'-phenylene-bis(salicylideneimine)). The preparation of stable complexes requires a careful choice of counter ions and reaction conditions. Notably the reaction of 1 with salophen(2-) in pyridine leads to immediate disproportionation, but in the presence of [18]crown-6 ([18]C-6) a stable complex forms. The solid-state structure of the four tetranuclear complexes, {[UO2(acacen)](4)[mu(8)-](2)[K([18]C-6)(py)]2} (3) and {[UO2(acacen)](4)[mu(8)-]}center dot 2[K([222])(py)] (4), {[UO2(salophen)](4)[mu(8)-K](2)[mu(5)-KI](2)[(K([18]C-6)])center dot 2 [K([18]C-6)-(thf)(2)]center dot 2I (5), and {[UO2(salen)(4)][mu(8)-Rb](2)[Rb([18]C-6)](2)) (9) ([222] = [222]cryptand, py =pyridine), presenting a T-shaped cation cation interaction has been determined by X-ray crystallographic studies. NMR spectroscopic and UV/Vis studies show that the tetranuclear structure is maintained in pyridine solution for the salen and acacen complexes. Stable mononuclear complexes of pentavalent uranyl are also obtained by reduction of the hexavalent uranyl Schiff base complexes with cobaltocene in pyridine in the absence of coordinating cations. The reactivity of the complex [(UO2)-O-V(salen)(py)][Cp*Co-2] with different alkali ions demonstrates the crucial effect of coordinating cations on the stability of cation cation complexes. The nature of the cation plays a key role in the preparation of stable cation cation complexes. Stable tetranuclear complexes form in the presence of K+ and Rb+, whereas Li+ leads to disproportionation. A new uranyl-oxo cluster was isolated from this reaction. The reaction of [UvO(2)(salen)(py)][Cp*Co-2] (Cp* = pentamethylcyclopentadienyl) with its U-VI analogue yields the oxo-functionalized dimer [UO2(salen)(py)](2)[Cp*Co-2] (8). The reaction of the {[UO2(salen)(4)][mu(8)-K](2)[K([18]C-6)](2)} tetramer with protons leads to disproportionation to U-IV and U-VI species and H2O confirming the crucial role of the proton in the U-V disproportionation.
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收藏
页码:14365 / 14377
页数:13
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共 67 条
  • [1] Na2Li8[(UO2)11O12(WO5)2]:: Three different uranyl-ion coordination geometries and cation-cation interactions
    Alekseev, Evgeny V.
    Krivovichev, Sergey V.
    Depmeier, Wulf
    Siidra, Oleg I.
    Knorr, Karsten
    Suleimanov, Evgeny V.
    Chuprunov, Evgeny V.
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (43) : 7233 - 7235
  • [2] Discrimination of metallosupramolecular architectures in solution by using diffusion ordered spectroscopy (DOSY) experiments: Double-stranded helicates of different lengths
    Allouche, Lionel
    Marquis, Annie
    Lehnl, Jean-Marie
    [J]. CHEMISTRY-A EUROPEAN JOURNAL, 2006, 12 (28) : 7520 - 7525
  • [3] Cation-cation interactions and antiferromagnetism in Na[Np(V)O2(OH)2]:: Synthesis, structure, and magnetic properties
    Almond, Philip M.
    Skanthakumar, S.
    Soderholm, L.
    Burns, Peter C.
    [J]. CHEMISTRY OF MATERIALS, 2007, 19 (02) : 280 - 285
  • [4] Reduction and selective oxo group silylation of the uranyl dication
    Arnold, Polly L.
    Patel, Dipti
    Wilson, Claire
    Love, Jason B.
    [J]. NATURE, 2008, 451 (7176) : 315 - U3
  • [5] Pentavalent uranyl complexes
    Arnold, Polly L.
    Love, Jason B.
    Patel, Dipti
    [J]. COORDINATION CHEMISTRY REVIEWS, 2009, 253 (15-16) : 1973 - 1978
  • [6] A CONVENIENT ENTRY INTO TRIVALENT ACTINIDE CHEMISTRY - SYNTHESIS AND CHARACTERIZATION OF ANI3(THF)4 AND AN[N(SIME3)2]3 (AN=U, NP, PU)
    AVENS, LR
    BOTT, SG
    CLARK, DL
    SATTELBERGER, AP
    WATKIN, JG
    ZWICK, BD
    [J]. INORGANIC CHEMISTRY, 1994, 33 (10) : 2248 - 2256
  • [7] CRYSTAL AND MOLECULAR-STRUCTURE OF [NN'-ETHYLENEBIS(SALICYLIDENEIMINATO)](METHANOL)DIOXOURANIUM
    BANDOLI, G
    CLEMENTE, DA
    CROATTO, U
    VIDALI, M
    VIGATO, PA
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1973, (21): : 2331 - 2335
  • [8] Highlights in uranium coordination chemistry
    Bart, Suzanne C.
    Meyer, Karsten
    [J]. ORGANOMETALLIC AND COORDINATION CHEMISTRY OF THE ACTINIDES, 2008, 127 : 119 - +
  • [9] Pentavalent Uranium Oxide via Reduction of [UO2]2+ Under Hydrothermal Reaction Conditions
    Belai, Nebebech
    Frisch, Mark
    Ilton, Eugene S.
    Ravel, Bruce
    Cahill, Christopher L.
    [J]. INORGANIC CHEMISTRY, 2008, 47 (21) : 10135 - 10140
  • [10] NMR investigation of non-covalent aggregation of coordination compounds ranging from dimers and ion pairs up to nano-aggregates
    Bellachioma, Gianfranco
    Ciancaleoni, Gianluca
    Zuccaccia, Cristiano
    Zuccaccia, Daniele
    Macchioni, Alceo
    [J]. COORDINATION CHEMISTRY REVIEWS, 2008, 252 (21-22) : 2224 - 2238