(trimethylsilyl)zirconocene chloride | 76772-61-7

• 英文名称: (trimethylsilyl)zirconocene chloride
• CAS: 76772-61-7
• 化学式: C₁₃H₁₉ClSiZr
• 分子量: 330.056
• InChiKey: WPQSADNEWLDFMX-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (trimethylsilyl)zirconocene chloride 在 H₂O 作用下， 以 水 为溶剂， 生成 (μ-oxo)bis[chlorobis(cyclopentadienyl)zirconium(IV)]
  参考文献：
  名称：

  Tilley, T. Don, Organometallics, 1985, vol. 4, # 8, p. 1452 - 1457

  摘要：

  DOI：
• 作为产物：
  描述：

  (η5-C5H5)2ZrCl(η2-COSiMe3) 以 not given 为溶剂， 生成 (trimethylsilyl)zirconocene chloride
  参考文献：
  名称：

  Insertion of carbon monoxide into a transition metal-silicon bond. X-ray structure of the silaacyl chloro(trimethylsilyl-.eta.2-carbonyl)bis(.eta.5-cyclopentadienyl)zirconium

  摘要：

  DOI：

  10.1021/ja00299a058

文献信息

• Reactions of carbon monoxide with trimethylsilyl and tris(trimethylsilyl)silyl derivatives of Group 4 metals. Synthesis, characterization, and reactivity of silaacyl complexes
  作者：Brian K. Campion、Jonathan Falk、T. Don Tilley

  DOI：10.1021/ja00241a023

  日期：1987.4

  monoxide in order to elucidate the factors involved in silyl migration to coordinated CO. The tendency of M-Si bonds in d/sup 0/ complexes to insert unsaturated substrates was expected to be greater than in previously studied complexes, since bond strengthening by metal-to-silicon ..pi..-donation cannot occur. Crystal structures of two zirconium silyl compounds indeed reveal rather long Zr-Si bonds. They

  他们关于早期过渡金属-甲硅烷基反应性的研究包括与一氧化碳的反应，以阐明甲硅烷基迁移到配位 CO 中涉及的因素。d/sup 0/ 配合物中的 M-Si 键插入不饱和底物的趋势是预计比以前研究的复合物更大，因为金属对硅的键合增强..pi..-donation 不会发生。两种锆甲硅烷基化合物的晶体结构确实揭示了相当长的 Zr-Si 键。他们在此报告了 -Si(SiMe/sub 3/)/sub 3/ 的锆和铪衍生物的制备以及这些和其他早期过渡金属甲硅烷基与 CO 的反应。
• Elimination of bis(trimethylsilyl)stannylene from tris(trimethylsilyl)stannylated zirconocene and hafnocene chlorides
  作者：Roland Fischer、Christoph Marschner

  DOI：10.1016/j.mencom.2022.01.016

  日期：2022.1

  Reactions of (Me3Si)3SnK with Cp2MCl2 (M = Zr, Hf) give the respective stannylated metallocene chlorides. These complexes display a tendency to eliminate bis(trimethylsilyl)-stannylene under Cp2M(Cl)SiMe3 formation.

  (Me 3 Si) 3 SnK 与 Cp 2 MCl 2 (M = Zr, Hf) 反应得到各自的亚锡烷基化茂金属氯化物。这些配合物在 Cp 2 M(Cl)SiMe 3形成下显示出消除双(三甲基甲硅烷基)-亚锡烷基的趋势。
• Chalcogenametallacyclohexadienes by thermally induced migratory ring enlargement of furyl- and thienylzirconocene complexes
  作者：Gerhard Erker、Ralph Petrenz、Carl Krueger、Frank Lutz、Astrid Weiss、Stefan Werner

  DOI：10.1021/om00040a040

  日期：1992.4

  Zirconocene dichloride reacts with 2 molar equiv of (2-furyl)lithium to give bis(2-furyl)zirconocene (1a). The (sigma-furyl)zirconocene complexes Cp2ZrR(2-furyl) (R = CH3, Ph, SiMe3) were similarly prepared by treatment of the respective Cp2Zr(R)Cl complexes with (2-furyl)lithium. Cp2Zr(SiMe3)(2-thienyl) was obtained from the reaction of Cp2Zr(SiMe3)Cl with (2-thienyl)lithium. The Cp2ZrR(2-furyl) complexes with R = 2-furyl, methyl, or phenyl all undergo an intramolecular high-temperature (greater-than-or-equal-to 180-degrees-C) sigma,sigma-exchange reaction to give the oxazirconacyclohexadienes Cp2 activated ZrOCH = CHCH = C(R) (2a-c). The 1a --> 2a rearrangement follows first-order kinetics in the temperature range 140-180-degrees-C and is characterized by the activation parameters DELTA-H double-ended-dagger = 30.9 +/- 2.0 kcal mol-1 and DELTA-S double-ended-dagger = -9 +/- 5 cal mol-1 K-1. The complexes Cp2Zr(SiMe3)(2-furyl) (1d) and Cp2Zr(SiMe3)(2-thienyl) (1e) undergo the analogous dyotropic rearrangements much faster. The 1d --> 2d isomerization is fast at 0-degrees-C and already takes place during the formation of 1d from Cp2Zr(SiMe3)Cl and (2-furyl)lithium. The activation parameters of the 1e --> 2e ring enlargement reaction of the (2-thienyl)metallocene system are DELTA-H double-ended-dagger = 20.4 +/- 2.0 kcal mol-1 and DELTA-S double-ended-dagger = -12 +/- 5 cal mol-1 K-1. The oxa- and thiazirconacyclohexadienes Cp2 activated Zr - X - CH = CHCH = C(SiMe3) (X = O, 2d; X = S, 2e) were characterized by X-ray diffraction. Complex 2d crystallizes in space group P1 with cell parameters a = 9.783 (1) angstrom, b = 11.514 (1) angstrom, c = 15.806 (1) angstrom, alpha = 96.27 (1)-degrees, beta = 101.64 (1)-degrees, gamma = 98.89 (1)-degrees, Z = 4, R = 0.037, and R(w) = 0.053. Complex 2e crystallizes in space group Cc with cell parameters a = 13.988 (4) angstrom, b = 30.774 (2) angstrom, c = 9.788 (4) angstrom, beta = 122.93 (1)-degrees, Z = 8, R = 0.034, and R(w) = 0.035. Both chalcogenazirconacyclohexadienes are monomeric in the solid state and exhibit nonplanar metallacyclic conformations with the metal-chalcogen vectors rotated significantly relative to the planes of the endocyclic conjugated diene moieties.
• Preparation and properties of (η-C5H5)2ZrCl[Si(CH3)3] and (η-C5H5)2Zr[Si(CH3)3]2; trimethylsilyl group transfer from mercury to zirconium
  作者：A.J. Blakeney、J.A. Gladysz

  DOI：10.1016/s0022-328x(00)92674-3

  日期：1980.12
• Koepf, Hartmut; Klapoetke, Thomas, Zeitschrift fur Naturforschung, Teil B: Anorganische Chemie, Organische Chemie, 1985, vol. 40, # 4, p. 447 - 449
  作者：Koepf, Hartmut、Klapoetke, Thomas

  DOI：——

  日期：——