NaC5H3(C4H9-t)2-1,3 | 125772-77-2

• 英文名称: NaC5H3(C4H9-t)2-1,3
• 英文别名: sodium 1,3-di-tert-butylcylopentadienate；sodium 2,5-di-tert-butylcyclopentadienyl；sodium 1,3-di(tert-butyl)cyclopentadienide；Na(Cp'')
• CAS: 125772-77-2
• 化学式: C₁₃H₂₁Na
• 分子量: 200.3
• InChiKey: HWSYXDPWSBAMHB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  14.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  NaC5H3(C4H9-t)2-1,3 、 三氯化铈 以 四氢呋喃 为溶剂， 以89%的产率得到[Ce(η-C5H3(t)Bu2-1,3)3]
  参考文献：
  名称：

  Activation of a CO bond by reaction of a tris(cyclopentadienyl)lanthanide complex with an alkali metal in dimethoxyethane (DME); crystal structures of [Ndη-C5H3(SiMe3)2-1,32(μ-OMe)2Li(DME)] and [{Ce(η-C5H3tBu2-1,3)2(μ-OMe)2]

  摘要：

  The reaction of [LnCp''(3)] [Ln = Ce, Cp'' = eta-C(5)H(3)(t)Bu(2)-1,3 or eta-C5H3(SiMe(3))(2)-1,3; or Ln = Nd and Cp'' = eta-C5H3(SiMe(3))(2)-1,3] with metallic lithium or potassium in dimethoxyethane (DME) at ambient temperature gave in high yield [{LnCp''(2)(mu-OMe)}(2)] [Ln = Ce and Cp'' = eta-C5H3(SiMe(3))(2)-1,3 (1) or eta-C(5)H(3)(t)Bu(2)-1,3 (2); or Ln = Nd and Cp'' = eta-C5H3(SiMe(3))(2)-1,3 (3)] or [NdCp''(2)(mu-OMe)(2)Li(DME)] (Cp'' = eta-C5H3(SiMe(3))(2)-1,3) (4). The crystal structures of complexes 2 and 4 are reported. Complex 4 is the first structurally characterized heterobimetallic lanthanocene-alkoxo-lithium.

  DOI：

  10.1016/0022-328x(95)00330-s

文献信息

• Crystal and molecular structures of bis(1,3-di-tert-butylcyclopentadienyl)cerium chloride and borohydride. First example of the bridging tetradentate BH4-group with two μ3-hydrogens: μ : η4-[(μ3-H)2B(μ2-H)2]
  作者：E.B. Lobkovsky、Yu.K. Gun'ko、B.M. Bulychev、V.K. Belsky、G.L. Soloveichik、M.Yu. Antipin

  DOI：10.1016/0022-328x(91)83122-k

  日期：1991.4

  Interaction between CeCl3 and two equivalents of (C5H3But2) Na leads to the complex [(η5-C5H3But2)2Ce(μ2-Cl)]2. (I). Crystals of 1 are rhombic, a = 13.032(3), b = 24.629(5), c = 17.044(3) Å, space group Pbnb, Z = 4, d = 1.630 g cm−3. Complex I reacts with one equivalent of LiBH4 to afford (η5-C5H3But2)2Ce[μ: η4-(η3-H)2B(μ2-H)2]}2 (II) which is isostructural to I. Two BH4 groups in complex II are tetradentate

  加入CeCl之间相互作用3和两个当量（C 5 H ^ 3卜吨2）的Na通向配合物[（η 5 -C 5 H ^ 3卜吨2）2的Ce（μ 2 -Cl）] 2。（我）。1的晶体是菱形的，a = 13.032（3），b = 24.629（5），c = 17.044（3）Å，空间群Pbnb，Z = 4，d = 1.630 g cm -3。配合物I与一当量的LiBH 4反应得到（η 5 -C 5 H ^ 3卜吨2）2的Ce [μ：η 4 - （η 3 -H）2 B（μ 2 -H）2 ]} 2（II），它是同构到I.两个BH 4个基团中的复合物II是四齿和含有两个μ 3 -和两个μ 2 -bridging氢。铈具有20e的环境。
• How big is a Cp? Cycloheptatrienyl zirconium complexes with bulky cyclopentadienyl and indenyl ligands
  作者：Andreas Glöckner、Heiko Bauer、Miyuki Maekawa、Thomas Bannenberg、Constantin G. Daniliuc、Peter G. Jones、Yu Sun、Helmut Sitzmann、Matthias Tamm、Marc D. Walter

  DOI：10.1039/c2dt12132h

  日期：——

  A combination of phase-transfer and traditional alkylation strategies has been employed to synthesise sterically encumbered 1,3-di(cyclohexyl) and 1,3-di(tert-butyl) substituted indenes in multi-gram quantities. These indenyl ligands and sterically demanding alkyl cyclopentadienyl ligands have been used to prepare a series of [(η7-C7H7)Zr(η5-L)] (L = Cp and Ind) complexes by straightforward salt metathesis between [(η7-C7H7)ZrCl(tmeda)] and the corresponding sodium indenide or cyclopentadienide. All of these Zr complexes have been characterized by elemental analysis, NMR spectroscopy and single crystal X-ray diffraction. The structural information derived from these studies was employed to evaluate the steric demand of these ligands in a realistic manner.

  采用相转移和传统烷基化策略的结合，合成了空间位阻较大的1,3-二(环己基)和1,3-二(叔丁基)取代的茚，并且产量达到数克。这些茚基配体和空间位阻较大的烷基环戊二烯基配体用于通过简单的盐交换反应，制备一系列[(η7-C7H7)Zr(η5-L)]（L = Cp 和 Ind）配合物，反应物为[(η7- )ZrCl(tmeda)]与相应的钠茚化物或环戊二烯化物。所有这些锆配合物都通过元素分析、核磁共振光谱和单晶X射线衍射进行了表征。这些研究获得的结构信息被用于以现实的方式评估这些配体的空间需求。
• Synthesis, structure and properties of divalent bis(di-tert-butylcyclopentadienyl)ytterbium complexes with diethyl ether and 1,2-dimethoxyethane
  作者：Alexey V Khvostov、Alexandr I Sizov、Boris M Bulychev、Sergei Ya Knjazhanski、Vitalii K Belsky

  DOI：10.1016/s0022-328x(98)00420-3

  日期：1998.5

  The reaction between YbI2 and 1,3-tBu2C5H3Na containing some 1,2-tBu2C5H3Na in diethyl ether or 1,2-dimethoxyethane afforded (1,3-tBu2C5H3)2Yb·OEt2 (1), (1,3-tBu2C5H3)2Yb·DME (2) and (1,2-tBu2C5H3)2Yb·DME (2a). The crystal structures of 1 and 2a were determined. Crystals of 1 are monoclinic: a=11.302(2) Å, b=19.018(4) Å, c=14.404(3) Å, β=90.41(3)°, dcalc=1.291 g cm−3, space group P21/n, z=4. Mean bond

  YbI之间的反应2和1,3-吨卜2 ç 5 ħ 3的Na含有一些1,2-吨卜2 ç 5 ħ 3的Na在乙醚或1,2-二甲氧基乙烷，得到（1,3-吨卜2 C 5 H 3）2 Yb·OEt 2（1），（1,3- t Bu 2 C 5 H 3）2 Yb·DME（2）和（1,2- t Bu 2 C 5 H3）2镱·DME（图2a）。确定了1a和2a的晶体结构。1的晶体是单斜晶体：a = 11.302（2）Å，b = 19.018（4）Å，c = 14.404（3）Å，β = 90.41（3）°，d calc = 1.291 g cm -3，空间群P 2 1 / n，z = 4。平均键距Yb–C，Yb–O和键角Cp–Yb–Cp分别为2.69（2）Å，2.430（14）Å和133.0°。2a的晶体是单斜晶体：a = 13.782（3）Å，b＝ 10.299（2），c＝ 10.849（2），β＝ 95.04（3）°，d
• Absolute Metal−Ligand σ Bond Enthalpies in Group 4 Metallocenes. A Thermochemical, Structural, Photoelectron Spectroscopic, and ab Initio Quantum Chemical Investigation
  作者：Wayne A. King、Santo Di Bella、Antonino Gulino、Giuseppe Lanza、Ignazio L. Fragalà、Charlotte L. Stern、Tobin J. Marks

  DOI：10.1021/ja9822815

  日期：1999.1.1

  Absolute metal−ligand σ bond enthalpies have been determined for a series of titanocene, zirconocene, and hafnocene halides and dimethyls by iodinolytic titration calorimetry. Absolute metal−iodine bond disruption enthalpies were measured by iodination of the monomeric trivalent group 4 metallocenes Cptt2TiI, (Me5C5)2TiI, Cptt2ZrI, and Cptt2HfI (Cptt = η5-1,3-di-tert-butylcyclopentadienyl). Iodinolysis

  已经通过碘分解量热法测定了一系列二茂钛、二茂锆和二茂铪卤化物和二甲基的绝对金属-配体 σ 键焓。绝对金属-碘键断裂焓通过单体三价第 4 族金属茂 Cptt2TiI、(Me5C5)2TiI、Cptt2ZrI 和 Cptt2HfI（Cptt = η5-1,3-二叔丁基环戊二烯基）的碘化来测量。Cptt2ZrMe2 和 Cptt2HfMe2 的碘分解依次产生绝对 Zr-Me 和 Hf-Me 键焓。导出值 (kcal/mol) 为 D[Cptt2Ti(I)-I] = 40.6(5)；D[(Me5C5)2Ti(I)-I] = 52.3(6); D[Cptt2Zr(I)−I] = 58.0(5); D[Cptt2Hf(I)−I] = 61.2(4); D[Cptt2Zr-Me2] = 43(1); 和 D[Cptt2Hf−Me2] = 47.6(9)。D[Cptt2Zr(I)−(I)] ≈ D(I3Zr−I)
• New Complexes of Divalent Thulium with Substituted Phospholyl and Cyclopentadienyl Ligands
  作者：François Nief、Brice Tayart de Borms、Louis Ricard、Duncan Carmichael

  DOI：10.1002/ejic.200400784

  日期：2005.2

  stabilise the Tm-II ion with phospholyl ligands lacking methyl groups at the 3 and 4 positions, the following ligand precursors were prepared: sodium 2,5-di-tert-butylphospholyl [Na(Htp)] (3) and sodium 2,5-bis(trimethylsilyl)phospholyl [Na(Hsp)] (8). Because of its similar steric bulk, we also decided to use sodium di-tert-butylcyclopentadienyl jNaCp(tt) (9) as a ligand precursor. Compound 3 was obtained

  为了尝试使用在 3 和 4 位缺少甲基的磷酰配体来稳定 Tm-II 离子，制备了以下配体前体：2,5-二叔丁基磷酰钠 [Na(Htp)] (3)和 2,5-双（三甲基甲硅烷基）磷酸钠 [Na(Hsp)] (8)。由于其空间体积相似，我们还决定使用二叔丁基环戊二烯基 jNaCp(tt) (9) 作为配体前体。通过 2,5,2',5'-四叔丁基-1,1'-二磷酸 (2) 的 PP 键的钠裂解获得化合物 3。在 1,4-二碘-1,4-双(三甲基甲硅烷基)丁-1,3-二烯 (4) 中进行卤素-锂交换，然后与 PhPCl2 反应得到 1-苯基-2,5-双(三甲基甲硅烷基)磷 (5 ）。用锂金属处理 5 然后用碘氧化处理得到 2,5,2',5'-四（三甲基甲硅烷基）-1,1' -diphosphole (7) 可以通过钠处理转化为 8。在乙醚中用 [TmI2(THF)(3)] 处理 3、8 和 9 产生三种新的有机铥