2-[Bis[2-[tert-butyl(dimethyl)silyl]azanidylethyl]amino]ethyl-[tert-butyl(dimethyl)silyl]azanide;uranium(4+);chloride | 183054-80-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 2-[Bis[2-[tert-butyl(dimethyl)silyl]azanidylethyl]amino]ethyl-[tert-butyl(dimethyl)silyl]azanide;uranium(4+);chloride
• CAS: 183054-80-0
• 化学式: C₂₄H₅₇ClN₄Si₃U
• 分子量: 759.482
• InChiKey: HLZJTFJIDLWTSD-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  5.43
• 重原子数：
  33
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  6.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-[Bis[2-[tert-butyl(dimethyl)silyl]azanidylethyl]amino]ethyl-[tert-butyl(dimethyl)silyl]azanide;uranium(4+);chloride 在 LiPh 作用下， 以 正戊烷 为溶剂， 以66%的产率得到C24H56N4Si3U, monoclinic
  参考文献：
  名称：

  Synthesis of a highly strained uranacycle: molecular structures of organometallic products arising from reduction, oxidation and protonolysis

  摘要：

  The reaction of [U(NN3')I] [NN3' = N(CH2CH2NSiMe2Bu')(3)] with Group 1 and 2 metal alkyls gives, via metalation of a methylsilyl group, a highly strained metallacycle [U(bit-NN3')] in high yield. The molecular structure of this compound shows that it has an unusually long U-C bond (ca. 2.75 Angstrom) and additional C-H ... M agostic interactions. On exposure of the complex in solution to H-2(2) the methylsilyl groups and the metallacyclic UCH2Si group are deuterated, leaving the tert-butyl and methylene groups intact. The analogous thorium metallacycle is prepared from the reactions of [Th(NN3')Cl], or by attempted reduction of [Th(NN3')I] with potassium metal in pentane. Attempted reduction of [U(NN3')I] in a similar manner in toluene gave a high yield of a fascinating dimeric metallacyclic anion {[K(eta(6)-C6H5Me)][U(bit -NN3')]}(2), which was characterised by X-ray crystallography. The authenticity of this compound as U(III) is established by near-IR spectroscopy, and also by its production from the reaction of the neutral uranacycle [U(bit-NN3')] with potassium. A mechanism for the formation of the anion is postulated. Its reaction with benzyl chloride led to oxidation to the parent uranacycle. Oxidation of [U(bit-NN3')] with air or oxide sources leads to formation of an ore-bridged dimer with intermonomer metalated methylsilyl groups and pentavalent uranium centres. Reactions of [U(bit-NN3')] with a range of acids HX occur rapidly, reprotonating the previously metalated methylsilyl group and forming complexes [U(NN3')X]. For example, lutidinium hydrochloride, diethylamine and tert-butanol gave [(NN3')UCl], [(NN3')U(NEt2)] and [(NN3')U(OBut)], respectively. Reactions with carbon acids were also successful. For example, beta-hydropyridines gave eta(2)-dehydropyridyl complexes. One of these, [U(NN3')(eta(2)-NC5H4)], is shown in the first X-ray crystallographic study of such an actinide complex to contain an essentially planar U(eta(2)-NC5H4) unit. Monosubstituted alkynes react with the uranacycle in a similar manner to give eta(1)-alkynyls. The molecular structure of one example shows that the U-C=C unit is bent (156 degrees) in contrast to other structurally characterised non-bridging alkynyls of the f-elements. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(99)00453-2
• 作为产物：
  描述：

  在 lutidine hydrochloride 作用下， 以 not given 为溶剂， 生成 2-[Bis[2-[tert-butyl(dimethyl)silyl]azanidylethyl]amino]ethyl-[tert-butyl(dimethyl)silyl]azanide;uranium(4+);chloride
  参考文献：
  名称：

  Synthesis of a highly strained uranacycle: molecular structures of organometallic products arising from reduction, oxidation and protonolysis

  摘要：

  The reaction of [U(NN3')I] [NN3' = N(CH2CH2NSiMe2Bu')(3)] with Group 1 and 2 metal alkyls gives, via metalation of a methylsilyl group, a highly strained metallacycle [U(bit-NN3')] in high yield. The molecular structure of this compound shows that it has an unusually long U-C bond (ca. 2.75 Angstrom) and additional C-H ... M agostic interactions. On exposure of the complex in solution to H-2(2) the methylsilyl groups and the metallacyclic UCH2Si group are deuterated, leaving the tert-butyl and methylene groups intact. The analogous thorium metallacycle is prepared from the reactions of [Th(NN3')Cl], or by attempted reduction of [Th(NN3')I] with potassium metal in pentane. Attempted reduction of [U(NN3')I] in a similar manner in toluene gave a high yield of a fascinating dimeric metallacyclic anion {[K(eta(6)-C6H5Me)][U(bit -NN3')]}(2), which was characterised by X-ray crystallography. The authenticity of this compound as U(III) is established by near-IR spectroscopy, and also by its production from the reaction of the neutral uranacycle [U(bit-NN3')] with potassium. A mechanism for the formation of the anion is postulated. Its reaction with benzyl chloride led to oxidation to the parent uranacycle. Oxidation of [U(bit-NN3')] with air or oxide sources leads to formation of an ore-bridged dimer with intermonomer metalated methylsilyl groups and pentavalent uranium centres. Reactions of [U(bit-NN3')] with a range of acids HX occur rapidly, reprotonating the previously metalated methylsilyl group and forming complexes [U(NN3')X]. For example, lutidinium hydrochloride, diethylamine and tert-butanol gave [(NN3')UCl], [(NN3')U(NEt2)] and [(NN3')U(OBut)], respectively. Reactions with carbon acids were also successful. For example, beta-hydropyridines gave eta(2)-dehydropyridyl complexes. One of these, [U(NN3')(eta(2)-NC5H4)], is shown in the first X-ray crystallographic study of such an actinide complex to contain an essentially planar U(eta(2)-NC5H4) unit. Monosubstituted alkynes react with the uranacycle in a similar manner to give eta(1)-alkynyls. The molecular structure of one example shows that the U-C=C unit is bent (156 degrees) in contrast to other structurally characterised non-bridging alkynyls of the f-elements. (C) 1999 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0022-328x(99)00453-2

文献信息

• Complexes of Triamidoamines with the Early Actinides. Synthetic Routes to Monomeric Compounds of Tetravalent Uranium and Thorium Containing Halide and Amide Ligands
  作者：Paul Roussel、Nathaniel W. Alcock、Rita Boaretto、Andrew J. Kingsley、Ian J. Munslow、Christopher J. Sanders、Peter Scott

  DOI：10.1021/ic990563f

  日期：1999.8.1

  [Li(3)(NN'(3))(THF)(3)] [NN'(3) = N(CH(2)CH(2)NSiMe(2)Bu(t))(3)] with AnCl(4) (An = U, Th) followed by sublimation gives monomeric [An(NN'(3))Cl]. Reaction of these complexes with SiMe(3)X (X = Br, I) gives [An(NN'(3))X]. The amido derivatives [An(NN'(3))(NEt(2))] are prepared from H(3)(NN'(3)) and [U(NEt(2))(4)] and from [Th(NN'(3))Cl] and [Li(NEt(2))]. In each case, the complexes [U(NN'(3))X] (X

  锂化三酰氨基胺[Li（3）（NN'（3））（THF）（3）] [NN'（3）= N（CH（2）CH（2）NSiMe（2）Bu（t） ）（3）]与AnCl（4）（An = U，Th），然后升华，得到单体[An（NN'（3））Cl]。这些配合物与SiMe（3）X（X = Br，I）反应得到[An（NN'（3））X]。酰胺衍生物[An（NN'（3））（NEt（2））]由H（3）（NN'（3））和[U（NEt（2））（4）]和[Th （NN'（3））Cl]和[Li（NEt（2））]。在每种情况下，复合物[U（NN'（3））X]（X = Cl，Br，I，NEt（2））均通过X射线晶体学显示含有三酰胺对称的三酰胺基配体。金属中心。由于铀原子从三个酰胺基氮原子的赤道平面移出了大约20个，从而使结构从三角形双锥体中变形了。0.8Å。配体主链以一种方式变形，以致使叔丁基二甲基甲硅烷基包围金属原子的赤道平面，
• Triamidoamine complexes of the actinides; from mixed-valence bimetallics to dinitrogen activation
  作者：Paul Roussel、Nigel D. Tinker、Peter Scott

  DOI：10.1016/s0925-8388(98)00043-7

  日期：1998.6

  reversible conversion to [U(NN' 3 )} 2 (μ 2 -η 2 :η 2 -N 2 )], the first dinitrogen complex of an actinide. The molecular structure as determined by X-ray crystallography shows that the dinitrogen ligand is side-on bonded to the two uranium centres and that the N-N bond length is essentially the same as that in free dinitrogen. This, and variable temperature magnetic data are consistent with the formulation

  淡绿色三(叔丁基二甲基甲硅烷基氨基乙基)氨基}氯铀(IV) [U(NN' 3 )Cl]与钾的还原得到紫色混合价(III/IV)二聚体[U(NN' 3 )} 2 - μ-Cl]，尽管 X 射线晶体学无法区分该化合物中的两个金属原子，但其他数据与存在不同的三价和四价中心一致。该物种的仔细分级升华允许分子裂化成 [U(NN' 3 )Cl] 和紫色 [U(NN' 3 )]。后一种物质与二氮气体反应以可逆地转化为 [U(NN' 3 )} 2 (μ 2 -η 2 :η 2 -N 2 )]，即锕系元素的第一种二氮络合物。X 射线晶体学确定的分子结构表明，二氮配体侧向键合到两个铀中心，NN 键长与游离二氮中的键长基本相同。该和可变温度磁数据与该化合物作为铀 (III) 的简单路易斯碱加合物的配方一致。基于二氮 π p 轨道是比 σ p 轨道对三价铀更好的 σ 供体，解释了侧向键合而不是端侧键合的偏好。
• Structure and reactions of a metallacyclic complex containing a remarkably long uranium–carbon bond
  作者：Rita Boaretto、Paul Roussel、Andrew J. Kingsley、Ian J. Munslow、Christopher J. Sanders、Nathaniel W. Alcock、Peter Scott

  DOI：10.1039/a903783g

  日期：——

  The intramolecular metalation of a β-silyl methyl group in [UN(CH2CH2NSiMe2But)3}(CH2Ph)] occurs rapidly, despite the conformational demands of the triamidoamine ligand, to produce a highly strained metallacycle (U–C ca. 2.75 Å); this complex reacts cleanly with a range of carbon and other acids to give, for example, an alkynyl with a bent (156°) U–CC unit.

  尽管三酰胺胺配体对构象有要求，但[UN(CH2CH2NSiMe2But)3}(CH2Ph)]中β-硅甲基的分子内金属化反应仍迅速发生，生成高度紧张的金属环（U-C约2.75 Å）；该复合物与一系列碳酸和其他酸发生清洁反应，例如，生成具有弯曲（156°）U-CC单元的炔基。
• A mixed-valence uranium(III/IV) bimetallic; structure, magnetism and reactivity
  作者：Paul Roussel、Peter B. Hitchcock、Nigel Tinker、Peter Scott

  DOI：10.1039/cc9960002053

  日期：——

  Reduction of [tris(tert-butyldimethylsilylamidoethyl)-amino]chlorouranium(IV)[L3UCl] with potassium gives the crystallographically characterised mixed-valence (III/IV dimer [L3U)2-µ-Cl] which acts as a source of trivalent uranium giving pentavalent [L3UN-SiMe3] on reaction with trimethylsilylazide.

  用钾还原[三（叔丁基二甲基硅酰胺乙基）-氨基]氯钛(IV)[L3UCl]可得到具有晶体学特征的混合价（III/IV）二聚体[L3U)2-µ-Cl]，该二聚体可作为三价铀的来源，在与三甲基硅烷基氮化物反应时产生五价[L3UN-SiMe3]。
• Roussel, Paul; Hitchcock, Peter B.; Tinker, Nigel D., Inorganic Chemistry, 1997, vol. 36, # 25, p. 5716 - 5721
  作者：Roussel, Paul、Hitchcock, Peter B.、Tinker, Nigel D.、Scott, Peter

  DOI：——

  日期：——