[Nb(η(5)-C5H4(SiClMe2))Cl4] | 202872-76-2

• 英文名称: [Nb(η(5)-C5H4(SiClMe2))Cl4]
• 英文别名: [Nb(η(5)-C5H4-SiMe2Cl)Cl4]；Nb(η⁵-C₅H₄SiMe₂Cl)Cl₄；(η5-C5H4SiMe2Cl)niobium(V)Cl4；Nb(η(5)-C5H4(SiMe2Cl)Cl4；[Nb(η5-C5H4SiMe2Cl)Cl4]；Nb(η5-C5H4SiMe2Cl)Cl4
• CAS: 202872-76-2
• 化学式: C₇H₁₀Cl₅NbSi
• 分子量: 392.413
• InChiKey: UNFVLFWBTDOLSI-UHFFFAOYSA-J

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(SiClMe2))Cl4] 、 邻苯二胺 在 三乙胺 作用下， 以 甲苯 为溶剂， 反应 3.0h， 以81%的产率得到Nb{η⁵-C₅H₄SiMe₂-κNC₆H₄-2-κNH₂}Cl₃
  参考文献：
  名称：

  制备N取代的铌配合物的合适方法-控制过程的因素研究

  摘要：

  的氯代甲硅烷基取代的环戊二烯基化合物铌[铌（η的反应5 -C 5 H ^ 4森达2 Cl）的氯4 ]（1用1个当量）。2-甲氧基乙胺，3-甲氧基丙胺，烯丙胺和在甲苯中的特异性，得到相应的胺加合物[Nb的（η 5 -C 5 H ^ 4森达2 Cl）的{NH 2（CH 2）Ñ OME}氯4 ]（Ñ = 2 ，2 ; 3，3）和[Nb的（η 5 -C 5 H ^ 4森达2 Cl）（NH 2 CH 2 CH = CH 2）Cl 4 ]（4）。相反，用1,2-苯二胺类似的反应用的Nb-Cl键的氨解和酰氨基胺化合物的形成前进[Nb的（η 5 -C 5 H ^ 4森达2 Cl）的（NHC 6 H ^ 4 ‐2‐κNH 2）Cl 3 ]（5）。当这样的反应在2当量的存在下进行时。在另外的碱的作用下，它们通过伯胺基团的双重去质子化和单一产物的形成而进行，单一产物的结构取决于侧基供体端基的配位能力。因此，获得

  DOI：

  10.1002/ejic.201601360
• 作为产物：
  描述：

  1-(chlorodimethylsilyl)-1-(trimethylsilyl)cyclopentadiene 、 五氯化铌 以 甲苯 为溶剂， 以90%的产率得到[Nb(η(5)-C5H4(SiClMe2))Cl4]
  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

文献信息

• Amido−Imido Niobium Complexes with Chloro−Silyl- and Amino−Silyl-Functionalized Cyclopentadienyl Ligands
  作者：M. Isabel Alcalde、M. Pilar Gómez-Sal、Pascual Royo

  DOI：10.1021/om9806491

  日期：1999.2.1

  silicon-bonded chlorine at the unsaturated niobium center. Benzylation of [Nbη5-C5H4-SiMe2(NHtBu)}(CH2Ph)Cl(NtBu)] with Mg(CH2Ph)2·2THF gives [Nbη5-C5H4-SiMe2(NHtBu)}(CH2Ph)2(NtBu)], which also results from reaction of the chloro−silyl derivative [Nb(η5-C5H4-SiMe2Cl)(CH2Ph)2(NtBu)] with NH2tBu. The dichloro−imido complex [Nb(η5-C5H4-SiMe2Cl)Cl2(NtBu)], readily obtained from [Nb(η5-C5H4-SiMe2Cl)Cl4], also

  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
• Synthesis and Reactivity of Oxametallacyclic Niobium Compounds by Using α,β‐Unsaturated Carbonyl Ligands
  作者：Rocío A. Arteaga‐Müller、Javier Sánchez‐Nieves、Pascual Royo、Marta E. G. Mosquera

  DOI：10.1002/ejic.200800060

  日期：2008.5

  We gratefully acknowledge the Ministerio de Educacion y Ciencia (MEC) (project MAT2007-60997) and the Direccion General de Universidades e Investigacion (DGUI) – Comunidad de Madrid (programme S-0505/PPQ-0328 COMAL-CM) (Spain) for financial support. R. A. A.-M. acknowledges MEC for a fellowship.

  我们衷心感谢教育与科学部长（MEC）（项目 MAT2007-60997）和大学与调查总局（DGUI）-马德里自治区（计划 S-0505/PPQ-0328 COMAL-CM）（西班牙）经济支持。RAA-M。承认 MEC 的奖学金。
• Cyclopentadienyl-Silyl-Amido versus Imido Niobium Complexes. The Role of Additional Amine Functionalities: A Combined Experimental and Theoretical Study
  作者：M. Carmen Maestre、Marta E. G. Mosquera、Heiko Jacobsen、Gerardo Jiménez、Tomás Cuenca

  DOI：10.1021/om701003t

  日期：2008.3.1

  [Nb(η5-C5H4SiMe2Cl)N(CH2)3NMe2}Cl2] (4a). However, treatment of 1 with 3 equiv of N-methylpropylene diamine in the absence of NEt3 gives the imido complex [Nb(η5-C5H4SiMe2Cl)N(CH2)3NHMe}Cl2] (4b). The reaction of 1 with 0.5 equiv of NH2(CH2)3NH2 in the presence of 2 equiv of NEt3 proceeds with the formation of the tethered dinuclear diimido compound [Nb(η5-C5H4SiMe2Cl)Cl2}2μ-N(CH2)3-η-N}] (5a). Analogous dinuclear

  的氯代甲硅烷基取代的环戊二烯基铌化合物的反应[Nb的（η 5 -C 5 H ^ 4森达2 Cl）的氯4 ]（1）用1个当量丙二胺或ñ在甲苯中2当量网的存在-methylpropylenediamine 3得到的环戊二烯基甲硅烷基酰氨基胺衍生物〔铌η 5 -C 5 H ^ 4森达2 -η-N（CH 2）3 -η-NHR}氯3〕（R = H，3A ; Me中，图3b） 。与此相反，使用了类似的反应Ñ，Ñ -dimethylpropylene二胺区域专一性产生了亚氨基化合物[Nb的（η 5 -C 5 H ^ 4森达2 Cl）的N（CH 2）3 NME 2 }氯2 ]（图4a）。然而，治疗的1与3当量的Ñ在不存在网的-methylpropylene二胺3给出了酰亚胺络合物[Nb的（η 5 -C 5 H ^ 4森达2 Cl）的N（CH 2）3 NHMe}氯2 ]（4b）。反应1用0.5当量的NH
• Aryl-imido niobium complexes with chloro-silyl and aryl-η-amidosilyl cyclopentadienyl ligands: X-ray structure of the constrained-geometry compound [Nb(η5-C5H4SiMe2-η1-NAr)(NAr)Cl] (Ar=2,6-Me2C6H3)
  作者：Rocío Arteaga-Müller、Javier Sánchez-Nieves、Pascual Royo、Marta E.G. Mosquera

  DOI：10.1016/j.poly.2005.02.027

  日期：2005.8

  Reactions of the magnesium imides [Mg(NAr)(THF)](6) (Ar = 2,6-Me2C6H3, 1a; Ph, 1b) with [(NbCpCl4)-Cl-Cl] (CPCl = eta(5)-C5H4 (SiMe2Cl)) afforded the imido complexes [(NbCpCl2)-Cl-Cl(NAr)] (Ar = 2,6-Me2C6H3, 2a; Ph, 2b) in good yield. Compound 2a reacted with excess LiNH(2,6-Me2C6H3) to give the silyl-eta-amido complex [Nb(eta(5)-C5H4SiMe2-eta(1)-NAr)Cl(NAr)] (Ar = 2,6-Me2C6H3, 3a). Hydrolysis of the Si-Cl bond of compounds 2a and 2b yielded the dinuclear complexes [NbCl2(NAr)}(2)(eta(5)-C5H4SiMe2)(2)(mu-O)}] (Ar = 2,6-Me2C6H3, 4a; Ph, 4b), respectively. All of the new compounds reported were characterized by NMR spectroscopy and the molecular structure of 3a was determined by X-ray diffraction methods. (c) 2005 Elsevier Ltd. All rights reserved.
• Cyclopentadienyl-Silyl-Amido Niobium Complexes Prepared by a Transmetalation Reaction Using Ti{η⁵-C₅H₄SiMe₂-η-N(CH₂)₂NRR‘}Cl₂
  作者：M. Carmen Maestre、Vanessa Tabernero、Marta E. G. Mosquera、Gerardo Jiménez、Tomás Cuenca

  DOI：10.1021/om0505312

  日期：2005.11.1

  Reaction of Tieta(5)-C5H4SiMe2-eta-N(CH2)(2)NRR'}Cl-2 with Nb(eta(5)-C5H4SiMe2Cl)Cl-4 affords the tethered heterodinuclear complexes TiCl2eta(5)-C5H4SiMe2-eta-N(CH2)(2)-K-NRR'}Nb(eta(5)-C5H4SiMe2-Cl)Cl-4, which are thermally unstable in solution and evolve to render an equimolar mixture of Ti(eta(5)-C5H4SiMe2Cl)Cl-3 and the corresponding cyclopentadienyl-amido niobium compounds, Nbeta(5)-C5H4SiMe2-eta-N(CH2)(2)NRR'}Cl-3. These compounds are straightforwardly obtained from the reaction of Nb(eta(5)-C5H4SiMe2Cl)Cl-4 with 1 equiv of the appropriate diamine, NH2(CH2),-NRR', in the presence of 2 equiv of NEt3, in high yield. In this reaction, the presence of the functional pendant chain plays a central role not only in determining the course of the reaction but also in stabilizing the final product, from both an electronic and a steric point of view. The molecular structure of Nbeta(5)-C5H4SiMe2-eta-N(CH2)(3)-eta-NH2]Cl-3 has been determined by X-ray diffraction methods.