(η(5):η(1)-C5H4SiMe2N(t)Bu)ZrCl2 | 184899-34-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (η(5):η(1)-C5H4SiMe2N(t)Bu)ZrCl2
• 英文别名: Zr(η(5):η(1)-C5H4SiMe2NtBu)Cl2；ZrCl2(η**(5)-C5H4)SiMe2-η**(1)-NtBu)；[Zr(η5-C5H4SiMe2-η1-N(t)Bu)Cl2]；tert-butyl-[cyclopenta-2,4-dien-1-yl(dimethyl)silyl]azanide;dichlorozirconium(2+)
• CAS: 184899-34-1
• 化学式: C₁₁H₁₉Cl₂NSiZr
• 分子量: 355.494
• InChiKey: PRMYIKRJTVQITL-UHFFFAOYSA-L

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：

  (η(5):η(1)-C5H4SiMe2N(t)Bu)ZrCl2 、 trans-Li(C5H3(SiMe3)(SiMe2CH2CHCH2)) 以 甲苯 为溶剂， 以94%的产率得到
  参考文献：
  名称：

  混合二甲硅烷基取代的环戊二烯衍生物和相应的锆、钼和钨化合物

  摘要：

  混合二甲硅烷基取代的环戊二烯 C 5 H 4 [Si-Me 2 (CH=CHCH 3 )](SiMe 3 ) (2) 通过 C 5 H 5 ( SiMe 2 Cl)。类似的烯烃系环戊二烯 C 5 H 4 [SiMe 2 (CH 2 CH=CH 2 )](SiMe 3 ) (3) 已通过传统的复分解路线从 Li[C 5 H 4 -(SiMe 3 )] 和氯代烯丙基硅烷SiMe 2 (CH 2 CH=CH 2 )Cl。相应的混合二甲硅烷基取代的环戊二烯基锂盐Li[C 5 H 3 -SiMe 2 R-3-SiMe 3 ] [R = CH = CHCH 3 (顺+反-4)；R=CH 2 CH=CH 2 (5)]用于分离手性锆化合物[ZrX(η 5 -C 5 H 4 SiMe 2- η 1 -NtBu)-(η 5 -C 5 H 3 -1- SiMe 2 R-3-SiMe 3 )] [X = Cl，R

  DOI：

  10.1002/ejic.201000394
• 作为产物：
  描述：

  三甲基氯硅烷 、 Zr(NEt2)4 在 C₅H₅Si(CH₃)2NHC(CH₃)3 作用下， 以 甲苯 为溶剂， 生成 (η(5):η(1)-C5H4SiMe2N(t)Bu)ZrCl2
  参考文献：
  名称：

  钛，锆和Ha的合成，Charakterisierung和PolymerisationseigenschaftenverbrückterHalbsandwichkomplexe des Titans；分子式[C 13 H 8 -SiMe 2 -N t Bu] ZrCl 2

  摘要：

  [Cp ＃ -SiMe 2 -N t Bu] MCl 2（Cp ＃ = C 13 H 8，C 9 H 6，C 5 H 4，C 5 H 3 t Bu; M描述了作为乙烯聚合的催化剂前体的＝ Zr，Hf）。该复合物通过1 H-，13 C-，29 Si-，15 N-和14 N-NMR光谱表征。从[C 13 H 8 -SiMe 2得到-N t Bu] ZrCl 2的X射线结构。研究了催化剂的活性和聚合物的性能。讨论了催化剂结构对聚合行为的影响。

  DOI：

  10.1016/s0022-328x(98)00527-0

文献信息

• Mono- and di-cyclopentadienyl zirconium derivatives containing the dimethylsilylcyclopentadienyl ligand. Agostic linear Si–H–Zr interaction in the molecular structure of [Zr{η5-C5H4(SiMe2H)}Cl3]2 †
  作者：Gemma Ciruelo、Tomás Cuenca、Rafael Gómez、Pilar Gómez-Sal‡、Avelino Martín ‡

  DOI：10.1039/b010221k

  日期：——

  Dimethylsilyl substituted mono- and di-cyclopentadienyl zirconium chlorides have been prepared and their reactions with amido and alkyl reagents studied. The silylcyclopentadienes C5H5(SiMe2H) 1, C5H4(SiMe2H)22 and C5H4(SiMe3)(SiMe2H) 3 can be prepared by reaction of Na(C5H5) with the appropriate chlorosilane reagent. The lithium salt Li[C5H4(SiMe2H)] reacts with ZrCl4 or [Zr(C5H5)Cl3] to give the metallocene complexes [Zr(C5H4R)C5H4(SiMe2H)}Cl2] (R = SiMe2H 4 or H 5) whereas the reaction of the disilylcyclopentadiene C5H4(SiMe2H)2 with ZrCl4 afforded the monocyclopentadienyl complex [ZrC5H4(SiMe2H)}Cl3] 6, which exchanges the Si–H and Zr–Cl bonds. The reaction of 6 with lithium amides produces different products depending on the basicity of the nitrogen atom and the steric demands of its amido substituents. The reaction with LiN(SiMe3)2 and LiNH(2,6-Me2C6H3) afforded the corresponding amido zirconium complexes [ZrC5H4(SiMe2H)}(NRR′)Cl2] (R = R′ = SiMe37; R = H, R′ = 2,6-Me2C6H38), but in the case of the reaction with LiNHtBu the known cyclopentadienylsilylamido derivative [Zr(η5,η1-C5H4SiMe2NtBu)Cl2] was formed. The monoamido, diamido and dialkyl dicyclopentadienyl complexes [Zr(C5H4R)C5H4(SiMe2H)}X(Y)] (R = SiMe2H 9 or H 10, X = Cl, Y = NHtBu; R = SiMe2H 11 or H 12, X = Y = NHtBu; R = SiMe2H 13 or H 14, X = Y = Me) have been synthesized by reaction of 4 and 5 with the appropriate amido or methyl reagent. Compound 9 reacts with a stoichiometric amount of water with selective hydrolysis of the Zr–amido bond to give the corresponding μ-oxo dinuclear complex [Zr[C5H4(SiMe2H)]2Cl}2(μ-O)] 15. The molecular structure of [ZrC5H4(SiMe2H)}Cl3] 6 was established by X-ray crystallography. Compound 6 is a dimer, in the solid state, in which dimerization occurs through Zr–H–Si agostic interactions and two chloride bridges.

  已经制备了二甲基硅烷取代的单环戊二烯基和二环戊二烯基锆氯化物，并研究了它们与氨基和烷基试剂的反应。通过Na(C5H5)与适当的氯硅烷试剂反应，可以制备硅基环戊二烯 (SiMe2H) 1、C5H4(SiMe2H)22和 (SiMe3)(SiMe2H) 3。锂盐Li[ (SiMe2H)]与ZrCl4或[Zr( )Cl3]反应，得到金属茂配合物[Zr( R) (SiMe2H)}Cl2]（R = SiMe2H 4或H 5），而二硅基环戊二烯 (SiMe2H)2与ZrCl4反应得到单环戊二烯基配合物[Zr (SiMe2H)}Cl3] 6，该配合物交换了Si–H和Zr–Cl键。6与锂胺反应，根据氮原子的碱性和其氨基取代基的立体要求，产生不同的产物。与LiN(SiMe3)2和LiNH(2,6-Me2C6H3)反应得到相应的氨基锆配合物[Zr (SiMe2H)}(NRR')Cl2]（R = R' = SiMe37；R = H，R' = 2,6-Me2C6H38），但在与LiNHtBu反应的情况下，形成了已知的环戊二烯基硅基氨基衍生物[Zr(η5,η1- SiMe2NtBu)Cl2]。通过4和5与适当的氨基或甲基试剂反应，合成了单氨基、二氨基和二烷基二环戊二烯基配合物[Zr( R) (SiMe2H)}X(Y)]（R = SiMe2H 9或H 10，X = Cl，Y = NHtBu；R = SiMe2H 11或H 12，X = Y = NHtBu；R = SiMe2H 13或H 14，X = Y = Me）。化合物9与化学计量水反应，选择性水解Zr–氨基键，得到相应的μ-氧二核配合物[Zr[ (SiMe2H)]2Cl}2(μ-O)] 15。通过X射线晶体学确定了[Zr (SiMe2H)}Cl3] 6的分子结构。化合物6在固态下是二聚体，二聚化通过Zr–H–Si暂稳相互作用和两个氯桥实现。
• Synthesis and Reactivity of [(Amidosilyl)cyclopentadienyl]titanium and -zirconium Complexes. X-ray Molecular Structure of [Zr{η⁵:η¹-C₅H₄SiMe₂(μ-O)}Cl₂{H₂N(CHMe)Ph}]₂
  作者：Santiago Ciruelos、Tomás Cuenca、Rafael Gómez、Pilar Gómez-Sal、Antonio Manzanero、Pascual Royo

  DOI：10.1021/om960606p

  日期：1996.12.24

  }Cl2]2 with elimination of alkyl isocyanate OCNR (R = tBu, (±)-CH(Me)Ph) as the unique organic product. Addition of 1 equiv of LiN(SiMe3)2 to a diethyl ether solution of [Zr(η5-C5H4SiMe2Cl)Cl3] (1b) gives the monoamido derivative [Zr(η5-C5H4SiMe2Cl)Cl2N(SiMe3)2}] (2b). The related reaction of the zirconium derivative 1b with LiNHtBu in the presence of NEt3 produces a mixture of two compounds, [Zr

  钛（IV）和锆（IV）的新型半夹心（amidosilyl）环戊二烯基复合物从氯代甲硅烷基取代的环戊二烯基前体的合成[M（η 5 -C 5 H ^ 4森达2 Cl）的氯3 ]（M =的Ti（1a），Zr（1b））。钛[Ti（η的反应5 -C 5 H ^ 4森达2 Cl）的氯3 ]（1A）与LiNHR净的存在3给出了钛[Ti（η 5：η 1 -C 5 ħ 4森达2 NR）氯2]（R = t Bu（2a），（±）-CH（Me）Ph（3a））络合物。类似地，加入2当量的LiN（森达的3）2至复杂1A，得到二酰胺衍生物钛[Ti（η 5 -C 5 H ^ 4森达2 Cl）的氯N（森达3）2 } 2 ] （图4a）。所述amidotitanium复杂钛[Ti（η 5：η 1 -C 5 ħ 4森达2 NH吨丁基）氯2（NH吨丁基）] （5a）中通过使1a与NH 2 t Bu以1：3的摩尔比反应以低收率制
• Stereoelectronic Influence of the Type of Bifunctional <i>a</i><i>nsa</i>-Monocyclopentadienyldimethylsilylamido Ligand on the Molecular Structures Displayed by Zirconium Dichloride and 1,4-Diphenylbutadiene Complexes
  作者：Leonie F. Braun、Thorsten Dreier、Matthew Christy、Jeffrey L. Petersen

  DOI：10.1021/ic040001i

  日期：2004.6.28

  functionality and an appended amido N donor have been prepared and structurally characterized. [(C(5)H(4))SiMe(2)(N-t-Bu)]ZrCl(2), 1, [(C(9)H(6))SiMe(2)(N-t-Bu)]ZrCl(2), 2, and [(C(5)Me(4))SiMe(2)(N-i-Pr)]ZrCl(2), 3, were prepared in two steps, with ligand chelation accomplished by an amine elimination reaction followed by treatment of the diamido Zr intermediate with an excess of SiMe(3)Cl. X-ray structural

  已经制备了一系列有机二氯化锆和1，4-二苯基丁二烯配合物，其特征在于具有环戊二烯基型官能团的双阴离子双官能配体和附加的酰胺N供体。[（C（5）H（4））SiMe（2）（Nt-Bu）] ZrCl（2），1，[[C（9）H（6））SiMe（2）（Nt-Bu）] ZrCl分两步制备（2），2和[[C（5）Me（4））SiMe（2）（Ni-Pr）] ZrCl（2），3，并通过胺消除反应完成配体螯合然后用过量的SiMe（3）Cl处理二酰胺Zr中间体。X射线结构分析表明，固态2是单体，而1和3是通过一对桥接氯化物连接的中心对称二聚体。中心Zr（2）（micro-Cl）（2）部分显示的不对称程度由一对独立桥Zr-Cl键距的变化表示，它们分别是1中的2.618（1）和2.657（1）A，以及3中的2.542（1）和2.745（1）A。[Mg（C（4）H（4）Ph（2））（THF）（3）]（n）（）与1、2、3和[（C（5）Me（4）
• Olefin isomerisation versus hydrozirconation: a case of a stable β-hydrogen-containing Zr-alkyl derivative
  作者：Cristina E. Petrisor、Luis Manuel Frutos、Obis Castaño、Marta E. G. Mosquera、Eva Royo、Tomás Cuenca

  DOI：10.1039/b803419m

  日期：——

  Details of the olefin isomerisation mechanism followed by monohydride constrained-geometry zirconium complexes have been clarified using the allyldimethylsilylcyclopentadienyl zirconium hydride model compound. DFT calculations on the model systems agree with the experimental results.

  烯烃异构化机理的细节，以及单氢化物约束几何锆配合物，已经使用烯丙基二甲基硅基环戊二烯基氢化锆模型化合物得到了澄清。模型系统的DFT计算结果与实验结果一致。
• A Study on Zr–Ir Multiple Bonding Active for C–H Bond Cleavage
  作者：Masataka Oishi、Masato Oshima、Hiroharu Suzuki

  DOI：10.1021/ic500258g

  日期：2014.7.7

  Zr-Ir hydrido complexes with ansa-(cyclopentadienyl)-(amide) as the supporting ligand in the zirconium fragment, e.g., ((LZrR)-Zr-1)(Cp*Ir)(mu-H)(3) [L-1 = Me2Si(eta(5)-C5Me4)((NBu)-Bu-t), R = Cl (5), Ph (7), Me (10), alkyl, and aryl] were designed, synthesized, and isolated as tractable early late heterodinuclear complexes. Despite the presence of the three supporting hydride ligands, Zr-Ir distances in the crystal structures of 5, alkyl, and aryl complexes [2.74-2.76 angstrom] were slightly longer than the sum of the element radii of Zr and Ir [2.719 angstrom]. These hydrocarbyl complexes displayed the thermolytic C H activation of a variety of aromatic compounds and several organometallic compounds. Also, the substrate scope and limitation in the Zr Ir system were studied. The regiochemical outcomes during the C H activation of pyridine derivatives and methoxyarenes suggested the in situ generation of a Lewis acidic active intermediate, i.e., ((LZr)-Zr-1)(Cp*IrH2) (III). The existence of III and relevant a-complex intermediates (LZr)-Zr-1(eta(2)-R-H)}(Cp*IrH2) (IIR) (R = Me, Ph) in the ligand exchange was demonstrated by the direct isolation of a Et3PO-adduct of III (39b) from 7 and kinetic studies. The structure of the direct Zr-Ir bonds in IIph, IIMe, III, and 39b were probed using computational studies. The unprecedented strong M-M' interactions in the early-late heterobimetallic (ELHB) complexes have been proposed herein.