[(η(5)-C5H3-1,3-(SiMe2CH2P(i-Pr)2)2)Li] | 149612-81-7

• 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: [(η(5)-C5H3-1,3-(SiMe2CH2P(i-Pr)2)2)Li]
• 英文别名: lithium;[[3-[di(propan-2-yl)phosphanylmethyl-dimethylsilyl]cyclopenta-1,4-dien-1-yl]-dimethylsilyl]methyl-di(propan-2-yl)phosphane
• CAS: 149612-81-7
• 化学式: C₂₃H₄₇LiP₂Si₂
• 分子量: 448.686
• InChiKey: USYJVCMMBLXWOZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.23
• 重原子数：
  28.0
• 可旋转键数：
  10.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 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：

  [(η(5)-C5H3-1,3-(SiMe2CH2P(i-Pr)2)2)Li] 、 以 甲苯 为溶剂， 以93%的产率得到(η5-C5H3-1,3-(SiMe2CH2P-i-Pr2)2)ZrCl3
  参考文献：
  名称：

  Synthesis, structure and fluxional behavior of [ν5-C5H3-1,3-(SiMe2CH2PPri202[ZrCl3−x Rx(R = Me, CH2Ph, x = 0, 1, 3)

  摘要：

  The addition of the potentially tridentate ligand [P(2)Cp]Li ([P(2)Cp]Li = (eta(5)-C5H3-1,3-(SiMe(2)CH(2)PPr(2)(i))(2))Li) to ZrCl4(THT)(2) (THT = tetrahydrothiophene) generates [P(2)Cp]ZrCl3. The X-ray crystal structure of this compound is described; crystals are orthorhombic, space group P2(1)2(1)2(1) having a = 14.282(2), b = 15.877(3), and c = 13.791(3) Angstrom, Z = 4; the structure was solved by the Patterson method and was refined by full-matrix least-squares to R = 0.032 and R(w) = 0.027 for 2907 reflections with I greater than or equal to 3 sigma(I). The solution behavior of this compound is consistent with the solid state structure in that the phosphine arms of the ligand remain coordinated. Alkylation of [P(2)Cp]ZrCl3 generates the corresponding alkyl complexes [P(2)Cp]ZrCl(3-x)R(x) (x = 1 or 3). In solution [P(2)Cp]Zr(CH(2)Ph)(3) exists in a four-coordinate pseudo-tetrahedral geometry with the two phosphine arms dangling. However, at low temperatures the complexes [P(2)Cp]ZrCl2(CH(2)Ph) and [P(2)Cp]ZrMe(3) exist as five-coordinate trigonal-bipyramidal structures with one phosphine coordinated and one phosphine uncoordinated. In these five-coordinate complexes, the coordinated phosphine exchanges with the uncoordinated phosphine via a dissociative pathway and/or an associative pathway depending on the number of hydrocarbyl substituents. The fluxional behavior of these complexes was studied by variable temperature P-31{H-1}, C-13{H-1} and H-1 NMR spectroscopy, and activation parameters were estimated.

  DOI：

  10.1016/0277-5387(94)00400-9

文献信息

• Preparation and Reactivity of Zirconium(III), Niobium(III), and Molybdenum(III) Complexes Stabilized by a Cyclopentadienyl Unit with Pendant Phosphine Donors
  作者：Michael D. Fryzuk、Laleh Jafarpour、Steven J. Rettig

  DOI：10.1021/om990096+

  日期：1999.9.1

  [i-PrP2Cp]Zr(CH3)Cl. The reaction of the Zr(III) complex [i-PrP2Cp]ZrCl2 with excess carbon monoxide results in disproportionation to the Zr(IV) complex, [i-PrP2Cp]ZrCl3, and the Zr(II) compound [i-PrP2Cp]Zr(CO)2Cl. This reaction is reversible, and upon removal of CO the starting material, [i-PrP2Cp]ZrCl2 is formed. The preparation of the diamagnetic Nb(III) complex [RP2Cp]NbCl2 is achieved by the reaction of NbCl3(DME)

  这与组4-6的三价第二排过渡金属的有机金属化学纸交易，即，锆，铌，和Mo，与配体cyclopentadienyldiphosphine [η 5 -C 5 H ^ 3 -1,3-（森2 CH 2 PR 2）2 ]，缩写为[ R P 2 Cp]（其中R = i -Pr和Ph）。中Zr（IV）配合物[我-镨P 2的Cp]的ZrCl 3所经历还原用Na / Hg至形成三价锆衍生物，[我-镨P 2的Cp]的ZrCl 2，其经历与将MeMgBr一个复分解反应，得到单甲基衍生物[我-镨P 2的Cp]的Zr（CH 3）氯。Zr（III）络合物的反应[ i-具有过量一氧化碳的Pr P 2 Cp] ZrCl 2导致歧化成Zr（IV）络合物，[ i-镨P 2的Cp]的ZrCl 3，和Zr的（II）化合物[我-镨P 2的Cp]的Zr（CO）2 CL上。该反应是可逆的，并且在移除CO的原料，[我-形成Pr P 2
• The first stable zirconium alkylidene complex formed via .alpha.-hydrogen abstraction: synthesis and x-ray crystal structure of [.eta.5-C5H3-1,3-(SiMe2CH2PPri2)2]Zr:CHPh(Cl)
  作者：Michael D. Fryzuk、Shane S. H. Mao、M. J. Zaworotko、L. R. MacGillivray

  DOI：10.1021/ja00065a072

  日期：1993.6