[Nb(η(5)-C5H4-SiMe2Cl)(CH2Ph)2(N(t)Bu)] | 202872-81-9

• 英文名称: [Nb(η(5)-C5H4-SiMe2Cl)(CH2Ph)2(N(t)Bu)]
• 英文别名: [Nb(η(5)-C5H4(SiClMe2))(CH2Ph)2(NtBu)]
• CAS: 202872-81-9
• 化学式: C₂₅H₃₃ClNNbSi
• 分子量: 503.989
• InChiKey: ZIRMLUHSSBMUFH-UHFFFAOYSA-N

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：

  [Nb(η(5)-C5H4-SiMe2Cl)(CH2Ph)2(N(t)Bu)] 、 叔丁胺 以 正己烷 为溶剂， 以90%的产率得到[Nb(η(5)-C5H4-SiMe2NH(t)Bu)(CH2Ph)2(N(t)Bu)]
  参考文献：
  名称：

  具有氯-甲硅烷基和氨基-甲硅烷基官能化的环戊二烯基配体的酰胺基亚氨基铌配合物

  摘要：

  氯-亚氨基配合物[Nb的（η 5 -C 5 H ^ 4 -SiMe 2 Cl）的（CH 2 PH）氯（N吨丁基）]经历当它与灵反应将Nb-Cl键的选择性取代吨卜，给予[Nb的（η 5 -C 5 H ^ 4 -SiMe 2 Cl）的（CH 2 PH）（NH吨卜）（N吨丁基）]，而在Si-Cl键优先反应用NH发生2吨卜，给[铌{η 5 -C 5 H ^ 4 -SiMe 2（NH吨丁基）}（CH 2PH）氯（N吨丁基）]，然后将其转化为[Nb的{η 5 -C 5 H ^ 4 -SiMe 2（NH吨丁基）}（CH 2 PH）（NH吨卜）（N吨丁基）]与NH 2 t Bu进一步反应。化学反应性的研究表明，[Nb的（η的自发变换5 -C 5 H ^ 4 -SiMe 2 Cl）的（CH 2 PH）（NH吨卜）（N吨丁基）]到[铌{η 5 -C 5 H ^ 4 -SiMe 2（NH tBu）}（CH 2 Ph）Cl（N

  DOI：

  10.1021/om9806491
• 作为产物：
  描述：

  dibenzylmagnesiumbis(tetrahydrofuran) 、 [Nb(η(5)-C5H4-SiMe2Cl)Cl2(N(t)Bu)] 以 正己烷 为溶剂， 以88%的产率得到[Nb(η(5)-C5H4-SiMe2Cl)(CH2Ph)2(N(t)Bu)]
  参考文献：
  名称：

  Chlorosilyl-Substituted Monocyclopentadienyl Niobium Chloro, Imido Chloro, and Benzyl Complexes. X-ray Molecular Structure of [{(NbCl₂)₂(μ-O)(μ-Cl)₂}{(η⁵-C₅H₄)₂(Me₂SiOSiMe₂)}]

  摘要：

  We report the synthesis of 1-(chloromethylphenylsilyl)cyclopentadie. The reaction of a toluene/CH2Cl2 suspension of NbCl5 with 1-(SiClMeX)-1-(SiMe3)C5H4 (X = Me, Ph) leads to the monocyclopentadienyl derivatives [M{eta(5)-C5H4(SiClMeX)}Cl-4] (X = Me, Ph) in 90 and 78% yields, respectively. Reaction of 1 equiv of water with [M(eta(5)-C5H4(SiClMe2))Cl-4] in toluene takes place with elimination of HCl, resulting in formation of the dinuclear niobium oxo derivative [((NbCl2)(2)(mu-O)(mu-Cl)(2))((eta(5)-C5H4)(2)(Me2SiOSiMe2)}]. Reaction of the complexes [M{eta(5)-C5H4(SiClMeX))Cl-4] with (LiNHBu)-Bu-t and NEt3 in toluene leads to the half-sandwich imido complexes [Nb{eta(5)-C5H4(siClMeX))Cl-2((NBu)-Bu-t)] (X = Me, Ph), which react at room temperature with 1 equiv of Mg(CH2Ph)(2)(THF)(2) to give the imido dibenzyl complexes [Nb{eta(5)-C5H4(siClMeX))(CH2Ph)(2)((NBu)-Bu-t)] (X = Me, Ph). The reaction of the chloro imido complexes [Nb{eta(5)-C5H4(SiClMeX))Cl-2((NBu)-Bu-t)] with excess Mg(CH2Ph)(2)(THF)(2) on heating for 2-3 days to 80-90 and 50-60 degrees C, respectively, takes place, affording the totally alkylated complexes [Nb{eta(5)-C5H4[si(CH2Ph)MeX])(CH2Ph)(2)((NBu)-Bu-t) (X = Me, Ph). The chloro benzyl derivative [Nb{eta(5)-C5H4(SiClMe2))(CH2Ph)Cl((NBu)-Bu-t)], which could not be prepared by addition of the stoichiometric amount of the alkylating agent, was isolated in quantitative yield by heating a mixture of the dichloro and dibenzyl complexes in toluene at 120 degrees C for 4 h. The 18-electron imido eta(2)-iminoacyl derivatives [Nb{(eta(5)-C5H4(SiMeXY))R((NBu)-Bu-t){eta(2)-C(CH2Ph=N- (2,6-Me2C6H3))] (R = CH2Ph, X = Cl, Y = Me, Ph; R = CH2Ph, X = CH2Ph, Y = Me, Ph; R Cl, X = Cl, Y = Me) are formed when the isocyanide CN(2,6-Me2C6H3) is added to a hexane solution of the benzylimido complexes. The molecular structure of the oxo complex [{(NbCl2)(2)(mu-O)(mu-Cl)(2)){(eta(5)-C5H4)(2)(Me2SiOSiMe2)}] has been determined by X-ray diffraction methods.

  DOI：

  10.1021/om970876n