Cp'2Zr{OC(SiPh3)(CN-2,6-Me2C6H3)}Cl | 141272-83-5

• 英文名称: Cp'2Zr{OC(SiPh3)(CN-2,6-Me2C6H3)}Cl
• CAS: 141272-83-5
• 化学式: C₄₈H₅₄ClNOSiZr
• 分子量: 815.725
• InChiKey: NPZNRVLLJFTNLE-UHFFFAOYSA-L

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：
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• 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：

  Cp'2Zr(η2-COSiPh3)Cl 、 2,6-二甲基苯基异腈 以 苯 为溶剂， 以64%的产率得到Cp'2Zr{OC(SiPh3)(CN-2,6-Me2C6H3)}Cl
  参考文献：
  名称：

  锆和ha的三苯基甲硅烷基，三苯基锗烷基和三苯基锡烷基衍生物的合成，表征和反应性

  摘要：

  The crystalline lithium silyl compound (THF)3LiSiPh3 (1) was isolated from the reaction of Ph3SiSiPh3 with lithium in tetrahydrofuran. This compound and tetrahydrofuran solutions of LiEPh3 (E = Ge, Sn) were used to prepare the complexes CpCp*Zr(EPh3)Cl (2, E = Si; 3, E = Ge), CpCp*Hf(EPh3)Cl (5, E = Si; 6, E = Ge; 7, E = Sn), Cp*2Zr(EPh3)Cl (8, E = Si; 9, E = Ge; 10, E = Sn), and Cp*2Hf(SiPh3)Cl (11). This method did not provide the zirconium stannyl complex CpCp*Zr(SnPh3)Cl (4) but instead gave the phenyl derivative CpCp*Zr(Ph)Cl via phenyl transfer. Compound 4 may be obtained via reactions of HSnPh3 with 2,3, or CpCp*Zr[Si(SiMe3)3]Cl. Reactions of 8 and 11 with MeMgBr gave Cp*2M(SiPh3)Me (12, M = Zr; 13, M = Hf). Hydrogenolysis of 2, 5, 8, and 11 provides routes to the corresponding hydrides CpCp*MHCl or Cp*2MHCl. Likewise, the reactions of 12 and 13 with hydrogen give Cp*2ZrH2 and Cp*2Hf(H)Me, respectively. The germyl and stannyl complexes were found to be significantly less reactive toward hydrogen. Reactions of 2-11 with PhSiH3 gave sigma-bond metathesis products in some cases and no reaction in other cases, such that the observed reactivity trends are CpCp*M > Cp*2M; Zr > Hf, M-Si > M-Ge > M-Sn. Carbonylation of 8 resulted in formation of Cp*2Zr(eta-2-COSiPh3)Cl (14), which reacts with HCl to give the thermally stable formylsilane Ph3SiCHO (15) and with 2,6-Me2C6H3NC to afford the ketenimine Cp*2Zr[OC(SiPh3)(CN-2,6-Me2C6H3)]Cl (16). The silyl complexes 5, 8, and 11 react with 2,6-Me2C6H3NC to give eta-2-iminosilaacyl insertion products, as does the germyl 3. However, no reaction is observed between 2,6-Me2C6H3NC and stannyl complexes 7 or 10. These investigations establish the reactivity trends M-SiPh3 > M-GePh3 > M-SnPh3 for sigma-bond metathesis processes with hydrogen and phenylsilane and for insertion reactions with carbon monoxide and 2,6-Me2C6H3NC. It is suggested that, for these analogues d0 metal silyl, germyl, and stannyl complexes, the energetics of the reactions are influenced primarily by the new E-element bond strengths of the products rather than by the d0 M-E bond strengths of the starting materials.

  DOI：

  10.1021/om00042a038