[Hf(η5-C5H5)(η5-C5H4SiMe2[CH2CH(CH2Ph)-η1-CH2])(O(t)Bu)] | 867194-17-0

• 英文名称: [Hf(η5-C5H5)(η5-C5H4SiMe2[CH2CH(CH2Ph)-η1-CH2])(O(t)Bu)]
• CAS: 867194-17-0
• 化学式: C₂₆H₃₆HfOSi
• 分子量: 571.147
• InChiKey: CBEGGBGOUKMSHO-HKPSJHCMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：

  [Hf(η5-C5H5)(η5-C5H4SiMe2(CH2CH=CH2))(CH2Ph)2] 、 三(五氟苯基)硼烷 、 potassium tert-butylate 以 四氢呋喃 、 甲苯 为溶剂， 以30%的产率得到[Hf(η5-C5H5)(η5-C5H4SiMe2[CH2CH(CH2Ph)-η1-CH2])(O(t)Bu)]
  参考文献：
  名称：

  Allyldimethylsilylcyclopentadienyl Hafnium Complexes:  Formation and Trapping of Hafnocenium Cations

  摘要：

  The mixed silyl-stannyl-cyclopentadiene C5H4[SiMe2(CH2CH=CH2)] [Sn(nBu)(3)] was synthesized by reaction of the lithium salt Li[C5H4{SiMe2(CH2CH=CH2)}] with the corresponding chlorotrialkyltin and then reacted with HfCl4 to prepare the monocyclopentadienyl complex [Hf{eta(5)-C5H4SiMe2(CH2CH=CH2)}Cl-3 center dot DME] (DME = dimethoxyethane). Reaction of this compound with Na(C5H5) or Li(C5H5) afforded low yields of the dichloro hafhocene [Hf(eta(5)-C5H5){eta(5)-C5H4SiMe2(CH2CH=CH2)}Cl-2], which was also isolated more efficiently by transmetalation of the lithium salt Li[C5H4{SiMe2(CH2CH=CH2)}] with [Hf(eta(5)-C5H5)Cl-3 center dot DME]. Alkylation of the mono- and dicyclopentadienyl complexes with MgCl(CH2Ph) or LiMe gave the tribenzyl monocyclopentadienyl [Hf(eta(5)-C5H4SiMe2(CH2CH=CH2)}(CH2Ph)(3)] or the dialkyl hafhocene derivatives [Hf(eta(5)-C5H5){eta(5)-C5H4SiMe2(CH2CH=CH2)R-2] (R = Me, CH2Ph). The reaction of the dibenzyl hafhocene with the Lewis acid B(C6F5)(3) was monitored by NMR spectroscopy at variable temperature. Formation of the hafhocenium cationic species [Hf(eta(5) -C5H5){eta(5)-C5H4SiMe2(CH2-eta(2)-CH=CH2)}(CH2Ph)(+) was initially observed, which then slowly transformed into the metallacyclic alkyl [Hf(eta(5)-C5H5){eta(5)-C5H4SiMe2CH2CH(CH2Ph)eta(1)-CH2}](+) cation, resulting from the benzyl migratory insertion of the allylic alkene moiety. Reaction of these intermediate cationic species with KOtBu gave the neutral dicyclopentadienyl hafhocene compounds [Hf(eta(5)-C5H5){eta(5)-C5H4SiMe2(CH2CH=CH2)}(CH2Ph)(OtBu)] and [Hf(eta(5)-C5H5){eta(5)-C5H4SiMe2[CH2CH(CH2Ph)-eta(1)-CH2]}(OtBu)], which were characterized by elemental analyses and NMR spectroscopy.

  DOI：

  10.1021/om050437l