A CONVENIENT ENTRY INTO TRIVALENT ACTINIDE CHEMISTRY - SYNTHESIS AND CHARACTERIZATION OF ANI3(THF)4 AND AN[N(SIME3)2]3 (AN=U, NP, PU)
A CONVENIENT ENTRY INTO TRIVALENT ACTINIDE CHEMISTRY - SYNTHESIS AND CHARACTERIZATION OF ANI3(THF)4 AND AN[N(SIME3)2]3 (AN=U, NP, PU)
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DOI：
10.1021/ic00088a030
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发表时间：
1994-05-11
影响因子：
4.6
通讯作者：
ZWICK, BD
中科院分区：
文献类型：
--
作者：
AVENS, LR;BOTT, SG;ZWICK, BD
过量的无氧化物的汞齐化铀金属切屑与元素碘或溴在配位溶剂中在0 ℃下反应，以65-80%的分离产率（THF =四氢呋喃，dme -1，2-二甲氧基乙烷，py =吡啶）得到深紫色UI 3（THF）4（1）、皇家蓝UBr 3（THF）4（2）、紫色UI 3（dme）2（3）或深黑色UI 3（PY）4（4）。镎和钚金属也可以在非质子配位溶剂中与元素碘干净地反应，以80-90%的分离产率得到黄橙色的NpI 3（THF）4（5）、灰白色的PuI 3（THF）4（6）和灰色的PuI 3（PY）4（7）。这些有机溶剂可溶的早期锕系元素的刘易斯碱加合物是各种无机和有机金属锕系元素络合物的前体。AnI_3（THF）_4配合物（U，Np，Pu）1，5和6在THF溶液中与3当量双（三甲基甲硅烷基）氨基钠反应，以80-90%产率得到挥发性、无溶剂的三-（甲硅烷基氨基）配合物An[N（SiMe_3）_2]_3 [An = U（8），Np（9），Pu（10）]。镎和钚的甲硅烷基酰胺是超铀元素均配酰胺基配合物的第一个例子。化合物1-10通过变温质子NMR、IR、UV/维斯/near-IR、热重和元素分析进行了表征。单晶X射线衍射数据显示1的中心铀原子与两个轴向碘配体（U-I = 3.111（2）埃（平均））和一个赤道碘配体（U-I = 3.167（2）埃）的五角双锥配位几何结构。所有四个THF配体都位于赤道平面内，平均U-0距离为2.52（1）埃。1的晶体数据（在23 ℃）：单斜空间群P2（1）/c，a = 8.750（3）埃，B = 16.706（16）埃，c = 17.697（7）埃，β = 93.64（3）度，V = 2582埃3，d（计算）= 2.33 g CM-3，Z = 4。
The reaction of excess, oxide-free amalgamated uranium metal turnings with elemental iodine or bromine in coordinating solvents at 0-degrees-C provides dark purple UI3(THF)4 (1), royal blue UBr3(THF)4 (2), purple UI3(dme)2 (3), or jet black UI3(PY)4 (4) in 65-80% isolated yield (THF = tetrahydrofuran, dme - 1,2-dimethoxyethane, py = pyridine). Neptunium and plutonium metal also react cleanly with elemental iodine in aprotic coordinating solvents to give yellow-orange NpI3(THF)4 (5), Off-white PuI3(THF)4 (6), and gray PuI3(PY)4 (7) in 80-90% isolated yields. These organic-solvent-soluble Lewis base adducts of early actinide tribalides are precursors to a variety of inorganic and organometallic actinide complexes. Reaction Of AnI3(THF)4 complexes (U, Np, Pu) 1, 5, and 6 in THF solution with 3 equiv of sodium bis(trimethylsilyl)amide provides the volatile, solvent-free tris-(silylamide) complexes An[N(SiMe3)2]3 [An = U (8), Np (9), Pu (10)] in 80-90% yields. The neptunium and plutonium silylamides are the first examples of homoleptic amido complexes of the transuranic elements. Compounds 1-10 have been fully characterized by variable-temperature proton NMR,IR,UV/vis/near-IR, thermal gravimetric, nd elemental analyses. Single-crystal X-my diffraction data for 1 revealed a pentagonal bipyramidal coordination geometry about the central uranium atom with two axial iodide ligands (U-I = 3.111(2) angstrom (average)) and one equatorial iodide ligand (U-I = 3.167(2) angstrom). All four THF ligands lie in the equatorial plane with an average U-0 distance of 2.52(1) angstrom. Crystal data for 1 (at 23-degrees-C): monoclinic space group P2(1)/c, with a = 8.750(3) angstrom, b = 16.706(16) angstrom, c = 17.697(7) angstrom, beta = 93.64(3)-degrees, V = 2582 angstrom3, d(calc) = 2.33 g CM-3, Z = 4.