carbanide,cyclopenta-1,3-diene,titanium(4+) | 107333-47-1

• 物质功能分类: 化学试剂 - 有机试剂 - 烯烃（环状与无环状）
• 英文名称: carbanide,cyclopenta-1,3-diene,titanium(4+)
• 英文别名: trimethyl(pentamethylcyclopentadienyl)titanium(IV)；trimethyl(η5-pentamethylcyclopentadienyl)titanium；pentamethylcyclopentadienyltitanium(IV) trimethyl；[(η(5)-pentamethylcyclopentadienyl)TiMe3]；(η(5)-pentamethylcyclopentadienyl)TiMe3；pentamethylcyclopentadienyltitanium trimethyl；(pentamethylcyclopentadienyl)TiMe3
• CAS: 107333-47-1
• 化学式: C₁₃H₂₄Ti
• 分子量: 228.214
• InChiKey: KBXCFLXEWFCLED-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

安全信息

• 危险等级：
  4.1
• 安全说明：
  S16
• 危险类别码：
  R10
• 海关编码：
  2931900090
• 包装等级：
  II
• 危险类别：
  4.1
• 危险品运输编号：
  UN 1325

反应信息

• 作为反应物：
  描述：

  carbanide,cyclopenta-1,3-diene,titanium(4+) 在 H₂O 作用下， 以 正己烷 为溶剂， 生成
  参考文献：
  名称：

  Hydrolytic studies on (η⁵-C₅Me₅)TiMe₃; X-ray structure of [(η⁵-C₅Me₅)TiMe(µ-O)]₃containing a Ti₃O₃ring

  摘要：

  (Î-5-C5Me5)TiMe3(2) 的连续水解首先产生 [(Î-5-C5Me5)TiMe2]2(µ-O)(3) ，然后产生 [(Î-5-C5Me5)TiMe(µ-O)]3(4) ；(4) 的晶体结构显示出一个 Ti3O3 环。

  DOI：

  10.1039/c39860001572
• 作为产物：
  描述：

  三甲基铝 、 syn-[(η5-pentamethylcyclopentadienyl)TiMe((cyclopentyl)7Si7O9(OSiMe3)O2)] 以 甲苯 为溶剂， 生成 carbanide,cyclopenta-1,3-diene,titanium(4+)
  参考文献：
  名称：

  Pentamethylcyclopentadienylmethyltitanium Silsesquioxanes and Their Zwitterionic Complexes with Tris(pentafluorophenyl)borane

  摘要：

  Reaction of [(eta(5)-C5Me5)TiMe3] With [(c-C5H9)(7)Si8O12(OH)] (SIPOSS) or [(c-C5H9)(7)Si7O9(OSiMe3)(OH)(2))] (DIPOSS') affords stoichiornetrically the half-sandwich titanium-disiloxy-nicthyl complexes [(eta(5)-C5Me5){(c-C5H9)(7)Si8O12O}(2) TiMe (1) and [(eta(5)-C5Me5) (c-C5H9)(7)Si7O9(OSiMe3)-O-2}TiMe] (2), respectively. Compound 2 consists orthe two stercoisonlers possessing the (eta(5)-C5Me5) ligand and OSiMe3 group in sYn- (2a) and anti-position (2b). The more abundant 2a (2a/2b approximate to 2:1) was isolated by fractional crystallization. Compounds I and 2a reacted rapidly with B(C6F5)(3) to give zwitterionic Complexes [(eta(5)-C5Me5) (c-C5H9)(7)Si8O12O}(2)Ti]((+)) (mu-Me)B(C6F5)(3)]((-)) 3 and syn-[eta(5)- C5Me5){(c-C5H9)(7)Si7O9(OSiMe3)O-2}Ti]((+))[(mu-Me)B(C6F5)(3)]((-)) (4a), respectively. Infrared spectra proved that 3 and 4awere thermally stable in the solid state, and the structure of 4a was determined by X-ray single-crystal analysis. In contrast, H-1, C-13, and F-19 NMR spectra of 3 in toluene C7D8 revutled that it was completely dissociated into initial components at 25 'C; however, the features of 3 were dominating already at -35 degrees C. On the other hand, 4a was dissociated only slightly at 25 degrees C. Stable ionic complexes 7 and 8 were prepared by reacting [PhNHMe2](+)[B(C6F5)(4)](-) With 1 and 2, respectively. Both 7 and 8 contained the molecule PhNMe, coordinated to the titanium cation, and 8 consisted of thes ' wi-and ami-isorners 8a and 81) in abundances found for 2a/2b. Analogous reaction of 1 and 2 with [Ph3C](+)[B(C6H5)(4)](-) afforded in1pUre ionic complexes 9and 10. When dissolved in the presence of PhNMe2, the amine Coordinated to the titanium cations, thus reproducing complexes 7 and 8a/8b, identified by H-1 NMR spectra. All compounds 1-10 were inactive in polymerization of styrene to syndiotactic polymer. A low activity was achieved by adding of 2 equiv of AlMe3 to 3 or 4.

  DOI：

  10.1021/om9007345
• 作为试剂：
  描述：

  氘代苯 、 α-chloronorbornene 在 carbanide,cyclopenta-1,3-diene,titanium(4+) 、 trityl tetrafluoroborate 作用下， 生成 exo-1-chloro-2-phenyl-d5-norbornane-7-d1
  参考文献：
  名称：

  受挫的 β-氯化物消除。亲电茂金属离子对催化α-氯冰片烯选择性芳烃烷基化

  摘要：

  通过活化 Cp*MMe3 (Cp* = C5Me5; M = Ti, Zr)、(CGC)MMe2 (CGC = C5Me4SiMe2NBut; M = Ti, Zr) 和 Cp2ZrMe2 与 Ph3C+B( C6F5)4- 在室温下催化芳香分子（苯、甲苯）与 α-氯降冰片烯的烷基化反应，区域选择性地提供 1:1 加成产物外型-1-氯-2-芳基降冰片烷（芳基 = C6H5 (1a)、C6H4CH3 ( 1b)) 收益良好。类似的氘标记产物 exo-1-chloro-2-aryl-dn-norbornane-7-d1 (aryl-dn = C6D5 (1a-d6), C6D4CD3 (1b-d8)) 通过 α-氯代降冰片烯的催化芳基化获得在苯-d6 或甲苯-d8 中。分离的离子对复合物如 (CGC)ZrMe(甲苯)+B(C6F5)4- 和 Cp*2ThMe+B(C6F5)4- 也催化 α-氯降冰片烯在甲苯-d8

  DOI：

  10.1021/ja047828w

文献信息

• Synthesis of polymetallic Group 4 complexes bridged by benzenediolate and triolate ligands. X-ray crystal structure of [{Ti(C5Me5)Cl2}2{μ-1,4-O(2,3-C6H2Me2)O}]
  作者：Silvia Arévalo、M.Rufina Bonillo、Ernesto de Jesús、F.Javier de la Mata、Juan C Flores、Rafael Gómez、Pilar Gómez-Sal、Paula Ortega

  DOI：10.1016/s0022-328x(03)00624-7

  日期：2003.9

  This paper reports the synthesis of polymetallic complexes in which two or three Group 4 metals are linked to a benzene core through oxo groups. Four methods have been evaluated for the synthesis of such derivatives: from the appropriated alcohol with (a) methyl complexes via methane elimination, (b) chloride compounds in the presence of a Lewis base, or (c) a zirconium hydride, and (d) from the lithium

  本文报道了多金属配合物的合成，其中两种或三种第4组金属通过氧代基与苯核连接。已评估了四种合成此类衍生物的方法：从适当的醇与（a）通过甲烷消除的甲基配合物，（b）在路易斯碱存在下的氯化物，或（c）氢化锆，和（d） ）由醇和氯化物络合物的锂盐组成。方法a已用于合成双金属和三金属（五甲基环戊二烯基）钛（IV）配合物[Ti（C 5 Me 5）Cl 2 } 2 μ-1,4-O（C 6 H 2 XY）O }]（X = Y = H（1）; X = H，Y = Me（2）; X = Y = Me（3）），[Ti（C 5 Me 5）Me 2 } 2 μ-1,4-O（C 6 H 2 Me 2）O}]（4）和[的Ti（C 5我5）X 2 } 3（μ 3 -1,3,5--C 6 H ^ 3 ö 3 ）]（X =氯（7）中，Me（8））从相应的氢醌1,4- -HO（2,3-C 6 H 2 XY）OH（X
• Titanium and zirconium compounds stabilized by coordination of heteroscorpionate [N,N,O]-donor ligands. Synthesis, characterization and polymerization activity
  作者：Giuseppe Alesso、Vanessa Tabernero、Tomás Cuenca

  DOI：10.1016/j.jorganchem.2012.07.004

  日期：2012.10

  suggested for the titanium complexes, while distorted octahedral geometries with a κ3-N,N,O coordination are proposed for the zirconium derivatives. Fluxional exchange between coordinated and non-coordinated pyrazolate rings is concluded in some zirconium compounds, depending on the electronic and steric effects imposed by the substituents of the heteroscorpionate ligands. Preliminary studies of catalytic

  双（吡唑-1-基）甲烷化合物[（2-羟基苯基）双（吡唑-1-基）甲烷（4）bpzmpH，（3,5-二叔丁基-2-羟基苯基）双（吡唑- 1-yl）甲烷（5）bpzt tBu2 pH，（2-羟基苯基）双（3,5-二甲基-吡唑-1-基）甲烷（6）Me2 bpzmpH，（3,5-二叔丁基-2 -（羟基苯基）双（3,5-二甲基-吡唑基）甲烷（7）Me2 bpzm tBu2 pH值，（2-羟基苯基）双（4-甲基-吡唑基）甲烷（8）Me bpzmpH和（3,5-二叔丁基）通过使相应的双（吡唑-1-基）酮（1），双（二）反应制备了作为异蝎子酸酯前体配体的-丁基-2-羟基苯基）双（4-甲基-吡唑基）甲烷（9）Me bpzm tBu2 pH ]。（3，5-二甲基吡唑-1-基）酮（2）和双（4-甲基吡唑-1-基）酮（3）与适当的水杨醛衍生物。已经研究了这些分子与含有环戊二烯基配体的钛和锆化合物的配位。合成TiCp
• Ethylene, Styrene, and α-Methylstyrene Polymerization by Mono(pentamethylcyclopentadienyl) (Cp*) Complexes of Titanium, Zirconium, and Hafnium:  Roles of Cationic Complexes of the Type [Cp*MR₂]⁺ (R = Alkyl) as both Coordination Polymerization Catalysts and Carbocationic Polymerization Initiators
  作者：Qinyan Wang、Ruhksana Quyoum、Daniel J. Gillis、Marie-José Tudoret、Dusan Jeremic、Brian K. Hunter、Michael C. Baird

  DOI：10.1021/om9501945

  日期：1996.1.23

  phosphine ligands). In contrast, much better olefin polymerization initiators result from abstraction of a methyl carbanion from Cp*MMe3 (Cp* = η5-pentamethylcyclopentadienyl) by B(C6F5)3, a reaction which gives cationic, 10-electron species of the type “[Cp*MMe2][BMe(C6F5)3]”. Of these, the complex [Cp*TiMe2][BMe(C6F5)3] (A) is an excellent initiator or initiator precursor for the polymerization of ethylene

  评估了钛，锆和ha的各种单环戊二烯基和单（五甲基环戊二烯基）络合物引发乙烯，苯乙烯和部分α-甲基苯乙烯聚合的能力。通常，对于CPMMe 3和CPMMe 2 OR类型的中性物种或[CPMR 2 L] +和[CPMR 2 L 2 ] +类型的阳离子12和14电子物种，几乎没有或没有活性，分别（CP =η 5 -环戊二烯基; R =烷基; L =胺，膦配体）。相反，更好的烯烃聚合引发剂是由CP * MMe 3提取甲基碳负离子产生的通过B（C 6 F 5）3（CP * =η5-五甲基环戊二烯基），该反应生成的阳离子类型为[[CP * MMe 2 ] [BMe（C 6 F 5）3 ]的10电子种类。其中，络合物[CP * TiMe 2 ] [BMe（C 6 F 5）3 ]（A）是用于乙烯和苯乙烯聚合的极好的引发剂或引发剂前体，分别导致高分子量聚乙烯和苯乙烯的高收率。无规立构（a-PS）和/或间同立构
• How Close Is Too Close? Polymerization Behavior and Monomer-Dependent Reorganization of a Bimetallic Salphen Organotitanium Catalyst
  作者：Anna M. Invergo、Shaofeng Liu、Rachel D. Dicken、Aidan R. Mouat、Massimiliano Delferro、Tracy L. Lohr、Tobin J. Marks

  DOI：10.1021/acs.organomet.8b00220

  日期：2018.8.13

  salphen Ti polymerization catalyst N,N′-1,2-phenylene[(salicylideneaminato)Ti(Cp*)Me2)]2 (2) is synthesized by reaction of salphen-H2 with Cp*TiMe3. Mononuclear [N-(2,6-diisopropyl)phenyl(salicylideneaminato)]Ti(Cp*)Me2 (1) serves as a control. Activation studies of 2 with cocatalyst Ph3C+B(C6F5)4– yield the cationic polymerization-inactive complex [N,N′-1,2-phenylene(salicylideneaminato)Ti(Cp*)]+B(C6F5)4–

  通过双酚-H 2与CP * TiMe 3的反应合成了双核双酚Ti聚合催化剂N，N'-1,2-亚苯基[（水杨酰亚胺基）Ti（CP *）Me 2）] 2（2）。单核[ N-（2,6-二异丙基）苯基（水杨酰亚氨基）] Ti（CP *）Me 2（1）作为对照。用助催化剂Ph 3 C + B（C 6 F 5）4进行2的活化研究–产生阳离子聚合无活性的配合物[ N，N'-1,2-苯（salicylideneaminato）的Ti（CP *）] + B（C 6 ˚F 5）4 - （4）和聚合活性的CP *时间2 + B（C 6 ˚F 5）4 - 。将2与CP * TiMe 3进行比较的聚合研究表明，在催化时间范围内，尽管2在乙烯气氛下保留了双金属特性，但它会迅速分解为4和CP * TiMe 2 +在1-己烯存在下。这些依赖单体的重组结果突出了烯烃聚合活化机理研究的重要性，同时为改进双金属催化剂设计提供了见识。
• Synthesis and X-ray Crystal Structures of β-Ketoiminate Complexes
  作者：Phillip Steiniger、Dennis Dittrich、Christoph Scheiper、Christoph John、Christoph Wölper、Stephan Schulz

  DOI：10.1002/zaac.201800321

  日期：2018.11.15

  equivalents of 2,6‐dimethylphenol yielded L1Do1Al(Me)O‐2,6‐Me2C6H3 (14) and L1Do1Al(O‐2,6‐Me2C6H3)2 (15). The complexes were characterized by elemental analysis, 1H, 13C NMR, and IR spectroscopy and single‐crystal X‐ray analysis (2, 4, 7, 10, 12–14).

  含侧臂供体官能化的三齿β-酮亚胺基配体的杂多锌配合物是从β-酮亚胺L1 / 2/3 Do1 / 2/3/4 H的金属化反应获得的[L1 = （OC（Me）C（H） C（Me）NCH 2 CH 2 Do）}，L2 = （OC（Me）C（H）C（Me）NCH 2 CH 2 CH 2 Do）}，L3 = （OC（OMe）C（H） C（Me）NCH 2 CH 2 Do）}；Do1 = NMe 2，Do2 = NEt 2 ; Do3 = Pyr，Do4 = OMe]，等摩尔量的Zn [N（SiMe 3）2 ] 2 [L1 Do1 ZnN（SiMe 3）2（1），L1Do2 ZnN（SiMe 3）2（2）]和ZnEt 2 [L1 Do3 ZnEt（3），L2 Do3 ZnEt（4），L3 Do1 ZnEt（5），L3 Do4 ZnEt（6）]。AlMe 3和Cp * MMe 3与L1 Do1 /