(pentamethylcyclopentadienyl)2ZrCl(PH(C6H2-2,4,6-t-Bu3)) | 158445-95-5

• 英文名称: (pentamethylcyclopentadienyl)2ZrCl(PH(C6H2-2,4,6-t-Bu3))
• CAS: 158445-95-5
• 化学式: C₃₈H₆₀ClPZr
• 分子量: 674.545
• InChiKey: LSAVWNVQEJZVCX-UHFFFAOYSA-M

计算性质

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

• 作为产物：
  描述：

  bis(pentamethylcyclopentadienyl)zirconium(IV) dichloride 、 (2,4,6-三-叔-丁基苯基)膦 在 BuLi 作用下， 以 四氢呋喃 为溶剂， 生成 (pentamethylcyclopentadienyl)2ZrCl(PH(C6H2-2,4,6-t-Bu3))
  参考文献：
  名称：

  立体诱导的PC键断裂：锆无取代基的磷配合物的途径。

  摘要：

  The reaction of Cp(2)ZrHCl with 1 equiv of K[PH(C6H2-2,4,6-t-Bu(3))] and excess KH in THF yields the dark red product [Cp(2)ZrH(P(C6H2-2,4,6-t-Bu(3)))K(THF)(2)](2), 4. The complex Cp*Zr-2(PH(C6H2-2,4,6-t-Bu(3)))Cl, 5, is derived from the reaction of Cp*2ZrCl2 with KPH(C6H2-2,4,6-t-Bu(3)). Generation of 5 via the reaction of Cp*2ZrCl2 with excess KH and phosphine results in P-C bond cleavage as evidenced by the formation of the diamagnetic species (Cp*Zr-2)(2)(mu-P-2), 6, and the paramagnetic compound (Cp*Zr-2)(2)(mu-P), 7. Compound 7 is the first dimetallaphosphallene to be structurally characterized. In an alternate synthetic route, reaction of 2 equiv of PH2(C6H2-2,4,6-t-Bu(3)) with (Cp*Zr-2(N-2))(2)(mu-N-2) yields P-C bond cleavage, as the species Cp*Zr-2[(PH)(2)], 8, is formed. Reaction of 8 with KH leads to the generation of species [Cp*Zr-2(P-2)][K(THF)(x)](2), 9, which reacts with Cp*2ZrCl2 to give 6 quantitatively. In a subsequent reaction, compound 6 undergoes reaction slowly with excess PH2(C6H2-2,4,6-t-Bu(3)) in the presence of KH to give compound 10. X-ray crystallographic study of 10 revealed the asymmetric unit to contain Cp*2ZrP3K(THF)(1.5). This species forms an infinite polymeric structure in the solid state. The nature of the bonding in species 7, 8, and 10 has been examined via EHMO calculations. The chemistry described herein demonstrates that high steric demands may induce P-C bond cleavage, thus offering a feasible metal-mediated route to substituent-free P complexes.

  DOI：

  10.1021/om00009a030

文献信息

• Substituent-Free P1, P2, and P3 Complexes of Zirconium
  作者：Maria C. Fermin、Jianwei Ho、Douglas W. Stephan

  DOI：10.1021/ja00092a090

  日期：1994.6