[η(5)-C5H3-1,3-(SiMe2CH2PPr(i)2)2]ZrCl2CH2C6H5 | 149612-78-2

• 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-(SiMe2CH2PPr(i)2)2]ZrCl2CH2C6H5
• 英文别名: dichlorozirconium(2+);[[3-[di(propan-2-yl)phosphanylmethyl-dimethylsilyl]cyclopenta-1,4-dien-1-yl]-dimethylsilyl]methyl-di(propan-2-yl)phosphane;methanidylbenzene
• CAS: 149612-78-2
• 化学式: C₃₀H₅₄Cl₂P₂Si₂Zr
• 分子量: 695.007
• InChiKey: LJNAXCOTPLQIQA-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  10.16
• 重原子数：
  37
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [η(5)-C5H3-1,3-(SiMe2CH2PPr(i)2)2]Zr(CH2C6H5)3 、 [η(5)-C5H3-1,3-(SiMe2CH2PPr(i)2)2]ZrCl2CH2C6H5 以 氘代苯 为溶剂， 生成 [η(5)-C5H3-1,3-(SiMe2CH2PPr(i)2)2]ZrCl(CH2C6H5)
  参考文献：
  名称：

  Mechanistic Studies of the Formation of Zirconium Alkylidene Complexes [η⁵-C₅H₃-1,3-(SiMe₂CH₂PPrⁱ₂)₂]ZrCHR(Cl) (R = Ph, SiMe₃)

  摘要：

  The reaction of [P2Cp]ZrCl3 (1) with 2 equiv of KCH2Ph generates an equilibrium mixture of alkyl complexes consisting of [P2Cp]ZrCl2(CH2Ph) (2), [P2Cp]ZrCl(CH2Ph)(2) (3), and [P2Cp]Zr(CH2Ph)(3) (4). Thermolysis of this mixture yields the alkylidene complex [P2Cp]Zr=CHPh(Cl) (5) in 85% overall yield. Kinetic studies reveal a composite mechanism that incorporates the above preequilibrium, followed by an intramolecular alpha-abstraction reaction of dibenzyl 3 which follows a first-order rate, with the rate parameters Delta H double dagger = 19(1) kcal mol(-1) and Delta S double dagger = -22(5) cal(-1) mol K-1. A kinetic isotope effect of 3.0(5) was measured at 70 degrees C for the perdeuterated analogue [P2Cp]ZrCl(CD2C6D5)2. The reaction of 1 with 2 equiv of LiCH2-EMe3 (E = C, Si) produces a similar equilibrium mixture as observed for the benzyl analogues, consisting of [P2Cp]ZrCl2(CH2EMe3) (7), [P2Cp]Zr(CH2EMe3)(3) (8), and [P2Cp]ZrCl(CH2EMe3)(2) (9). Thermolysis of this mixture yields [P2Cp]Zr=CHEMe3(Cl) (6). A kinetic analysis conducted on 9 (E = Si) indicated a first-order reaction from which the activation parameters Delta H double dagger = 6(1) kcal mol(-1) and Delta S double dagger = -62(5) cal mol(-1) K-1 were obtained. The results indicate that reaction rates follow the order CH2Ph > CH2SiMe3 > CH2CMe3, an exact reversal of the trend for the homoleptic Ta systems Ta(CH2R)(5). The role of phosphine coordination is discussed to account for this trend. A crystal structure determination obtained for 6b reveals an alpha-agnostic interaction and a structure analogous to that of 5.

  DOI：

  10.1021/ja982969h
• 作为产物：
  描述：

  (η5-C5H3-1,3-(SiMe2CH2P-i-Pr2)2)ZrCl3 、 以 甲苯 为溶剂， 生成 [η(5)-C5H3-1,3-(SiMe2CH2PPr(i)2)2]ZrCl2CH2C6H5
  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