trichloro[1,3-di(tert-butyl)cyclopentadienyl]zirconium | 161697-78-5

• 英文名称: trichloro[1,3-di(tert-butyl)cyclopentadienyl]zirconium
• 英文别名: Zr(η(5)-C5H3-t-Bu2-1,3)Cl3；[Zr(1,3-(t)Bu2-η(5)-C5H3)Cl3]；[Zr(η(5)-C5H3Bu(t)2)Cl3]；1,3-bis(tert-butyl)cyclopentadienylzirconium trichloride；1,3-bis(tert-butyl)cyclopentadienylzirkontrichlorid
• CAS: 161697-78-5
• 化学式: C₁₃H₂₁Cl₃Zr
• 分子量: 374.893
• InChiKey: CSQUVESULPIELT-UHFFFAOYSA-K

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：
  None

反应信息

• 作为反应物：
  描述：

  dibenzylmagnesiumbis(tetrahydrofuran) 、 trichloro[1,3-di(tert-butyl)cyclopentadienyl]zirconium 以 正己烷 为溶剂， 以85%的产率得到[Zr(1,3-(t)Bu2-η(5)-C5H3)(CH2Ph)3]
  参考文献：
  名称：

  Synthesis of bis (tert-butyl)cyclopentadienyl derivatives of titanium and zirconium. NMR spectra and dynamic behaviour of the base-free [Zr(1,3-tBu2-η5-C5H3)(CH2Ph)2]+ cation

  摘要：

  Reaction of Si(1,3-(t)Bu(2)-C5H3)Me(3) with MCl(4) (M = Ti, Zr) in toluene or hexane at room temperature affords the new trichloromonociclopentadienyl-type derivatives [M(1,3-(t)Bu(2)-eta(5)-C5H3)Cl-3] (M = Ti (2), Zr (3)]. Treatment of complexes 2 and 3 with appropriate alkylating reagents in hexane gives the 1,3-di(tert-butyl)cyclopentadienyl trialkyl titanium and zirconium complexes [M(1,3-(t)Bu(2)-eta(5)-C5H3)R(3)][M = Ti, R = CH3 (4), CH(2)Ph (5); M = Zr, R = CH3 (6), CH(2)Ph (7), CH(2)CMe(2)Ph (8)]. Interestingly, when 2 reacts with 3.1 equivalents of LiCH(2)CMe(2)Ph in hexane at room temperature the ring-tert-butyl-metallated complex [Ti(1-(t)Bu-3-CMe(2)CH(2)-eta(5)-C5H3) (CH(2)CMe(2)Ph)(2)] (9) was isolated in 90% yield. The cationic mono(1,3-di-(tert-butyl)cyclopentadienyl dibenzyl zirconium species [Zr(1,3-(t)Bu(2)-eta(5)-C5H3)(CH(2)Ph)(2)](+), generated in situ by reaction of the tribenzyl complex 7 with B(C6F5)(3) or [CPh(3)](+)[B(C6F5)(4)](-) reagents, is reported and their dynamic NMR behaviour in CD2Cl2 solutions at low temperatures is studied.

  DOI：

  10.1016/0022-328x(95)00116-8
• 作为产物：
  描述：

  氯化锆(IV) 、 rac-1,3-di(tert-butyl)-5-trimethylsilylcyclopentadiene 以 四氢呋喃 为溶剂， 生成 trichloro[1,3-di(tert-butyl)cyclopentadienyl]zirconium
  参考文献：
  名称：

  来自大块烷基环戊二烯基氯化锆的环壬四烯基-茚基转化和锆 (III) 三聚体

  摘要：

  已知钛、锆和铪三氯二（叔丁基）环戊二烯基配合物的结构测定 [Cp″MCl3] {Cp″ = η5-C5H3tBu2, M = Zr (2), Ti (3), Hf (4) } 在通过升华获得的晶体上显示固态的单体分子。与外消旋二（叔丁基）（三甲基甲硅烷基）环戊二烯基三氯化锆 5 不同，2,3-二异丙基-1,4-二甲基环戊二烯基三氯化锆 7 不是单体，因为它的挥发性低，并且存在两组相似的信号。核磁共振谱。2 或其 Cp"' 类似物 [(η5-C5H2tBu3-1,2,4)ZrCl3] (1) 与环壬四烯化钾的反应没有得到所需的环壬四烯基配合物 [Cp"' (C9H9)ZrCl2] 或其 Cp" 类似物，但茚基复合物 [Cp″′(C9H7)ZrCl2] (8) 和 [Cp″(C9H7)ZrCl2] (9)。

  DOI：

  10.1002/ejic.201300885

文献信息

• Neutral and cationic di(tert-butyl) cyclopentadienyl titanium, zirconium and hafnium complexes dynamic NMR study of the ligand-free cations [M(1,3-tBu2-η5-C5H3)(η5-C5H5)(CH3)]+ (M = Zr, Hf)
  作者：José Ignacio Amor、Tomás Cuenca、Mikhail Galakhov、Pilar Gómez-Sal、A. Manzanero、Pascual Royo

  DOI：10.1016/s0022-328x(97)00034-x

  日期：1997.5

  obtained as a mixture of syn- and anti-isomers as shown by NMR spectroscopic observations. The formation of (29) and (30) implies the stabilization of the 14-electron cationic intermediate by interaction with one methyl group of the neutral complexes (14) and (26). Complexes (27) and (28) undergo heterolytic dissociation of the Metal-MeB(C6F5)3 bonds, leading to the formation of the free [M(1,3-tBu2-η5

  含有二第4族金属配合物（叔丁基）环戊二烯基配位体（1,3-吨卜2 - η 5 -C 5 H ^ 3）已经被合成。1,3-和1,4-二（叔丁基）环戊二烯异构体的混合物与KH在THF中在-78°C下反应，得到盐K + [（1,3- t Bu 2 C 5 H 3）] -（THF）1-3 2为白色固体。用氯三甲基硅烷以1：1的摩尔比处理2，得到空气稳定的三甲基甲硅烷基环戊二烯基衍生物Si（1,3-t Bu 2 C 5 H 3）（CH 3）3 3。的甲硅烷基衍生物3是一个极好的前体的单环戊二烯三氯和锆化合物M（1,3-吨卜2 - η 5 -C 5 H ^ 3）氯3 [M =的Ti（4），锆（5）]。在NEt 3存在下将化学计量的水添加到4的甲苯溶液中，得到羰基三聚体化合物[Ti（1,3- t Bu 2 - η5 -C 5 H 3）Cl（μ- O）] 3 6。4与2equiv的反应。石灰，得到氯甲基衍生物的Ti（1
• π-H3C5(Me2Si) (Me2SiSiMe2)-π-C5H3: Ein neuartiger, zweifach verbrückter Dicyclopentadienyl-Ligand: Synthese und beispielhafter Einsatz in der Komplexchemie
  作者：Peter Jutzi、Ingrid Mieling、Beate Neumann、Hans-Georg Stammler

  DOI：10.1016/s0022-328x(97)00011-9

  日期：1997.8

  Deprotonation of dicyclopentadienyldimethylsilane with two equivalents of n-butyllithium and subsequent reaction with 1,2-dichlorotetramethyldisilane yields the double-bridged dicyclopentadiene H4C5(SiMe2)(Si2Me4)C5H4 (1 = H2L). Reaction of 1 with two equivalents of n-butyllithium leads to the dilithio compound Li-2 [H3C5(SiMe2)(Si2Me4)C5H3] (2 = Li2L) with the bridging dimethylsilyl and tetramethyldisilanyl group in 1,2 position (ortho-position) at each cyclopentadienyl unit 2 is used as starting material for the exemplary synthesis of the following metal complexes: Cp '' Cl2ZrLZrCl2Cp '' (3; Cp '' = 1,3-(t-Bu)(2)C5H3), Cp '' Cl2ZrLH (4); Me5C5RuLRuC5Me5 (syn: 5a; anti: 5b); syn-(CO)(2)CoLCo(CO)(2) (6). All compounds are characterized by spectroscopic and analytical data. X-ray crystal structures are presented for 1 and for 3. Stereochemical effects in metal complexes with the new unsymmetrically bridged dicyclopentadienyl ligand L are discussed.
• Dinuclear zirconium complexes with Me₂Si(C₅H₄)₂as bridging ligand. Molecular structure of [{Zr(η⁵-C₅H₃-Bu^t₂)Me}₂(µ-O){µ-Me₂Si(C₅H₄)₂}]
  作者：Gemma Ciruelo、Tomás Cuenca、Pilar Gómez-Sal、Avelino Martín、Pascual Royo

  DOI：10.1039/dt9950000231

  日期：——

  The reaction of Li-2[Me(2)Si(C5H4)(2)] with 2 equivalents of [ZrLCl(3)] (L = C(5)Me(5) or C(5)H(3)Bu(2)(t)) in toluene under reflux gave the known [Zr(C(5)Me(5))Cl-2}(2)mu-Me(2)Si(C5H4)(2)}] 1 and the new chloro derivative [Zr(C5H3-Bu(2)(t))Cl-2}(2)mu-Me(2)Si(C5H4)(2)}] 2 in good yields. Addition of 4 equivalents of LiMe (or MgMeCl) to a pentane solution of 1 or 2 afforded the tetramethyl derivatives [Zr(C5(M)e(5))Me(2)}(2)mu-Me(2)Si(C5H4)(2)}] 3 and [Zr(C(5)H(3)Bu(2)(t))Me(2)}(2)mu-Me(2)Si(C5H4)(2)}] 4. Compound 3 is extremely moisture sensitive leading to the mu-oxo dinuclear complex [Zr(C(5)Me(5))Me}(2)(mu-O)mu-Me(2)Si(C5H4)(2)}] 5, as demonstrated by H-1 NMR spectroscopy. Compound 4 reacted with water, in pentane or toluene, to give the mu-oxo dimethyl complex [Zr(C(5)H(3)Bu(2)(t))Me}(2)(mu-O)mu-Me(2)Si(C5H4)(2)}] 6. Further reaction of 6 with water in toluene gave an unidentified insoluble yellow powder through the intermediate formation of a mu-dioxo methyl complex 7, identified by H-1 NMR spectroscopy. The crystal structure of 6 has been determined by X-ray diffraction methods: monoclinic, space group P2(1)/n, a = 15.494(4), b = 13.338(3), c = 19.933(4) Angstrom, beta = 107.19(1)degrees and Z = 4. Complex 6 is a dimer produced by the interaction of two Zr(eta(5)-C(5)H(3)Bu(2)(t))Me units bridged by one oxygen atom and the Me(2)Si(C5H4)(2) group.