Synthesis and crystal structure of pentavalent uranyl complexes. The remarkable stability of UO2X (X = I, SO3CF3) in non-aqueous solutions

被引:81
作者
Berthet, Jean-Claude [1 ]
Siffredi, Gerald [1 ]
Thuery, Pierre [1 ]
Ephritikhine, Michel [1 ]
机构
[1] CEA Saclay, CEA, IRAMIS, Serv Chim Mol,CNRS,URA 331, F-91191 Gif Sur Yvette, France
关键词
CATION-CATION INTERACTIONS; N-HETEROCYCLIC CARBENE; N; N'-AROMATIC BIDENTATE LIGANDS; URANIUM AMIDE COMPOUNDS; F-ELEMENT; EQUATORIAL COORDINATION; ELECTRONIC-STRUCTURE; GROUP-1; SALTS; ACTINYL IONS; BASE RATIO;
D O I
10.1039/b820659g
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction of [UO2I2(THF)(3)] with KC5R5 (R = H, Me) or K2C8H8 in pyridine gave crystals of [{UO2(py)(5)}{KI2(py)(2)}](infinity) (1), which were desolvated under vacuum into pulverulent [UO2(py)(2.2)KI2] (2). Similar reactions with [UO2(OTf)(2)] afforded [UO2(py)(2.3)K(OTf)(2)] (3) as a powder and crystals of [{UO2(py)(5)}(2){K-3(OTf)(5)}center dot py](infinity) (4 center dot py), which were also obtained together with crystals of [{UO2(py)(5)}(2){K(OTf)(2)(py)(2)}][OTf]center dot py (5 center dot py) by treating [UO2(OTf)(2)] with KC4Me4P. Crystals of 6 center dot py, the thallium analogue of 5 center dot py, were isolated from the reaction of [UO2(OTf)(2)] and TlC5H5. Treatment of [UO2I2(THF)(3)] with LiCH2SiMe3 in pyridine afforded crystals of [{UO2(py)(5)}{Lil(py)(2)}][I] (7) while [UO2(OTf)(2)] reacted with the alkyllithium reagent in acetonitrile to give crystals of [{UO2(py)(5)}{Li-2(OTf)(3)}](infinity) (8) in pyridine. The crystal structures of 1, 4 center dot py, 5 center dot py, 6 center dot py, 7 and 8 revealed the presence of U=O -> M interactions (M = Li, K, Tl), and the rich diversity of these structures, from dinuclear (7) to 3D polymeric (4), is related to the distinct coordination numbers of the M+ ion and ligation modes of the bridging iodide and triflate ligands as well as the presence of U=O -> M interactions. The mononuclear complexes [UO2(OTf)(THF)(n)] (9) and [UO2(OTf)(Et2O)(0.5)] (10) were respectively obtained by reaction of [UO2(OTf)(2)] with KC5R5 in THF or LiCH2SiMe3 in Et2O, and were transformed into [UO2(OTf)(py)(2)] (11) in pyridine. Treatment of [UO2I2(THF)(3)] with TlC5H5 in pyridine afforded crystals of [UO2(py)(5)][I]center dot py (12 center dot py) which were desolvated under vacuum into the powder of [UO2I(py)(2.5)] (14). The same reaction in THF gave [UO2I(THF)(2.7)] (13) in powder form. Crystals of [UO2(CyMe4BTBP)(py)][OTf]center dot 1.5py (15.1.5py) and the powder of [UO2I(CyMe4BTBP)] (16) were obtained by treating [UO2(CyMeBTBP)X-2] (X = OTf, I) with KC5Me5 or TlC5H5, respectively The uranyl(v) chloride and nitrate compounds [UO2Cl(py)(3)] (17) and [UO2(NO3)(py)(3)] (18) were prepared by reaction of the uranyl(vi) precursors with TlC5H5 in pyridine; complex 18 was also obtained by treating 13 with TlNO3. Crystals of the neutral mononuclear complex [UO2(OTf(py)(4)] (19) were isolated from reaction of [UO2(OTf)(2)] with Me3SiC3H5 in acetonitrile. Similar reaction with [UO2Cl2(THF)(2)](2) in pyridine gave crystals of [UO2Cl2(py)(3)]. The crystal structures of 12 center dot py, 15.1.5py and 19 were determined; the structure of 15 was compared with that of the uranyl(vi) counterpart. All the uranyl(v) compounds are remarkably stable in pyridine solution; the IR absorption at 816 cm(-1) is attributed to the nu(asym) (U=O) of the ubiquitous [UO2(py)(5)](+) species.
引用
收藏
页码:3478 / 3494
页数:17
相关论文
共 105 条
  • [91] Metallocene organoactinide complexes
    Sharma, Manab
    Eisen, Moris S.
    [J]. ORGANOMETALLIC AND COORDINATION CHEMISTRY OF THE ACTINIDES, 2008, 127 : 1 - 85
  • [92] A short history of SHELX
    Sheldrick, George M.
    [J]. ACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES, 2008, 64 : 112 - 122
  • [93] Synthesis and reactivity of bis(imido) uranium(VI) cyclopentadienyl complexes
    Spencer, Liam P.
    Gdula, Robyn L.
    Hayton, Trevor W.
    Scott, Brian L.
    Boncella, James M.
    [J]. CHEMICAL COMMUNICATIONS, 2008, (40) : 4986 - 4988
  • [94] A theoretical study of the inner-sphere disproportionation reaction mechanism of the pentavalent actinyl ions
    Steele, Helen
    Taylor, Robin J.
    [J]. INORGANIC CHEMISTRY, 2007, 46 (16) : 6311 - 6318
  • [95] Activation of small molecules by U(III) cyclooctatetraene and pentalene complexes
    Summerscales, Owen T.
    Cloke, F. Geoffrey N.
    [J]. ORGANOMETALLIC AND COORDINATION CHEMISTRY OF THE ACTINIDES, 2008, 127 : 87 - 117
  • [96] CRYSTAL AND MOLECULAR-STRUCTURE OF TRIMERIC BIS(1,1,1,5,5,5-HEXAFLUOROPENTANE-2,4-DIONATO)DIOXOURANIUM(VI)
    TAYLOR, JC
    EKSTROM, A
    RANDALL, CH
    [J]. INORGANIC CHEMISTRY, 1978, 17 (11) : 3285 - 3289
  • [97] Complexation of a hexameric uranium(VI) cluster by p-benzylcalix[7]arene
    Thuéry, P
    Nierlich, M
    Souley, B
    Asfari, Z
    Vicens, J
    [J]. JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1999, (15): : 2589 - 2594
  • [98] Uranyl ion complexation by citric and tricarballylic acids:: hydrothermal synthesis and structure of two- and three-dimensional uranium-organic frameworks
    Thuéry, P
    [J]. CHEMICAL COMMUNICATIONS, 2006, (08) : 853 - 855
  • [99] Hetero(tri- and tetra-)nuclear complexes of uranyl and alkali metal (Li+, K+) ions with p-tert-butylhexahomotrioxacalix[6]arene
    Thuéry, P
    Masci, B
    [J]. POLYHEDRON, 2004, 23 (04) : 649 - 654
  • [100] Synthesis and crystal structure of 1:2 mixed uranyl/alkali metal ions (Li+, Na+, K+, Cs+) complexes of p-tert-butyltetrahomodioxacalix[4]arene
    Thuéry, P
    Masci, B
    [J]. DALTON TRANSACTIONS, 2003, (12) : 2411 - 2417