[Cp*Zr(SEt)3]2 | 166021-60-9

• 英文名称: [Cp*Zr(SEt)3]2
• 英文别名: [C5Me5Zr(ethanethiolato)3]2
• CAS: 166021-60-9
• 化学式: C₃₂H₆₀S₆Zr₂
• 分子量: 819.672
• InChiKey: DYGQOFLXHHEHDK-UHFFFAOYSA-H

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

• 作为产物：
  描述：

  Cp*ZrBz₃ 、 乙硫醇 以 not given 为溶剂， 生成 [Cp*Zr(SEt)3]2
  参考文献：
  名称：

  有机锆配合物作为末端炔烃的马尔科夫尼科夫选择性分子间氢硫醇化的催化剂：范围和机制

  摘要：

  使用 CGCZrMe(2) (CGC = Me(2)SiCp'' NCMe(3), Cp'' = C( 5)Me(4)), Cp*ZrBn(3) (Cp* = C(5)Me(5), Bn = 苄基), Cp*ZrCl(2)NMe(2), Cp*(2)ZrMe( 2)，并报道了 Zr(NMe(2))(4) 预催化剂。这些转化显示出高度马尔可夫尼科夫选择性，选择性高达 99%，通常产率大于 90%。该反应已在制备规模上以 72% 的分离产率和 99% 的马尔可夫尼科夫选择性进行了证明。由于已知的非有机金属自由基机制，有时会观察到抗马尔科夫尼科夫产物的混合物，这种机制可以通过添加自由基抑制剂来抑制。动力学研究表明，CGCZrMe(2) 介导的 1-戊硫醇和 1-己炔反应是催化剂浓度的一级反应，炔烃浓度的一级反应，较低浓度下硫醇反应的一级反应，但过渡到零-浓度 > 0.3 M 时的顺序。炔烃的氘标记产生

  DOI：

  10.1021/ja103979b

文献信息

• Chemical, Computational, and Structural Studies of Dimeric (Pentamethylcyclopentadienyl)zirconium Thiolate and Alkoxide Complexes
  作者：Richard H. Heyn、Douglas W. Stephan

  DOI：10.1021/ic00115a005

  日期：1995.5

  The compounds [Cp*Zr(SR)(2)(mu(2)-SR)](2)(R=Bz (6), Et (7)) are prepared via reaction of Cp*ZrCl3 with 3 equiv of the respective sodium thiolate. The NMR data of 6 are consistent with a symmetric dimer in which two thiolate ligands bridge two Zr centers and the pentamethylcyclopentadienyl ligands adopt a cisoid geometry. In the case of 7, a mixture of three isomers of the dimeric complex is observed (cisoid (syn) 7a, transoid (anti) 7b, and transoid (syn) 7c). These species have been characterized by high-field NMR as well as crystallography in the case of 7b. Reaction of 6 with PMe(3) results in the monomeric adduct Cp*Zr(SBz)(3)(PMe(3)) (8). Reaction of 6 with MeOH yields the transoid dimer species [Cp*Zr(OMe)(2)(mu-OMe)](2) (9). The species [Cp*Zr(SBz)](2)(mu(2)-SBZ)(3)(mu(3)-O)Li(THF) (10) is also prepared and structurally characterized. Molecular mechanics and EHMO calculations of models based on the structures of 7b and 9 infer that the planarity at the bridging S or O atoms in these dimers arises as a result of steric factors rather than pi-bonding. This view is supported to some extent by the crystallographic study of 10. Compound 7b crystallizes in the space group P $($) over bar$$ 1, with a=9.580(3) Angstrom, b=12.210(2) Angstrom, c=9.222(3) Angstrom, alpha=95.01(2)degrees, beta=108.55(2)degrees, gamma=72.62(2)degrees, V=976.0(5) Angstrom(3), and Z=1. Compound 9 crystallizes in the space group P2(1)/n, with a=12.540(3) Angstrom, b=9.691 (3) Angstrom, c=13.165(3) Angstrom, beta =107.16(2)degrees, V=1529.3(7) Angstrom(3), and Z=2. Compound 10 crystallizes in the space group P $($) over bar$$ 1, with a=12.907(8) Angstrom, b=22.270(6) Angstrom, c=11.610(8) Angstrom, alpha=99.81(3)degrees, beta=114.59(6)degrees, gamma=79.24(3)degrees, V=2965(3) Angstrom(3), and Z=2.