CpTiCl₂(N=CtBu₂) | 328122-49-2

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: CpTiCl₂(N=CtBu₂)
• 英文别名: (η⁵-cyclopentadienyl)TiCl₂(N=CtBu₂)；[Ti(η5-C5H5)(N=C(t-Bu)2)Cl2]；cyclopenta-1,3-diene;2,2,4,4-tetramethylpentan-3-ylideneazanide;titanium(4+);dichloride
• CAS: 328122-49-2
• 化学式: C₁₄H₂₃Cl₂NTi
• 分子量: 324.129
• InChiKey: PKHQPMSIDVXJNT-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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反应信息

• 作为反应物：
  描述：

  CpTiCl₂(N=CtBu₂) 、 甲基溴化镁 以 乙醚 为溶剂， 生成 carbanide;cyclopenta-1,3-diene;2,2,4,4-tetramethylpentan-3-ylideneazanide;titanium(4+)
  参考文献：
  名称：

  钛半夹心烯烃聚合催化剂中环戊二烯基和酮亚胺基配体的连接作用

  摘要：

  在各种条件下，研究了酮亚胺配体几何形状在Ti半三明治配合物中的作用以及其在烯烃聚合催化（乙烯，苯乙烯，1-己烯聚合和乙烯/ 1-己烯共聚）中的作用。[CpTiCl 2（N = C吨卜2）]（1 ; CP =η 5 -环戊二烯基）用作参考化合物用于与最近描述的络合物[比较{η 5 -C 5 H ^ 4 CME 2 CME 2 C（吨卜）= ñ -κ ñ }的TiCl 2 ]（2一）并且具有Cp和酮酰亚胺，之间的较长接头新衍生物[{η 5 -C 5 H ^ 4 CH 2 CH 2 CME 2 C（吨卜）= Ñ -κ Ñ }的TiCl 2 ]（9）。在含有Al基助催化剂（甲基铝氧烷，三异丁基铝）的体系中，分子内束缚的酮亚胺部分的存在会大大降低聚合活性。然而，在无铝体系中，两种类型的化合物都提供了活性聚合催化​​剂。值得注意的是，最近报道的活化系统Et 3 SiH / B（C 6 F 5）3是首次

  DOI：

  10.1002/cctc.201700498
• 作为产物：
  描述：

  三氯一茂钛 、 lithium (2,2,4,4-tetramethylpentan-3-ylidene)amide 以 甲苯 为溶剂， 以90%的产率得到CpTiCl₂(N=CtBu₂)
  参考文献：
  名称：

  The Mechanism of Methane Elimination in B(C₆F₅)₃-Initiated Monocyclopentadienyl-Ketimide Titanium and Related Olefin Polymerization Catalysts

  摘要：

  A new class of monocyclopentadienyl titanium olefin polymerization catalysts and their activation with B(C6F5)(3) is reported herein. Dichlorides Cp[Bu-t(R)C=N]TiCl2 {Cp = C5H5, R = Bu-t (1a); Cp = C5Me5, R = Bu-t (2a); Cp = C5Me4SiMe3, R = Bu-t (3a); Cp = C5Me5, R = CH2SiMe3 (4a); Cp = C5Me5, R = Me (5a)} were prepared in 50-92% yield from CpTiCl3 and Bu-t(R)C=NLi. Analogous dimethyl compounds 1b-5b were prepare via methylation of dichlorides a using MeMgBr in 89-92% yield. Dimethyl compound 6b (L = C5Me5, R = CH(SiMe3)(2)) was prepared directly from Cp*TiMe3 and Bu-t[(Me3Si)(2)CH]C=NH in 40% yield. Dynamic H-1 NMR studies showed that the ketimide ligands in compounds b rotate rapidly about Ti-N on the NMR time scale, with a a Delta G(double dagger) of 9.6(6) kcal mol(-1) or less. The mixed alkyl compound Cp*-[Bu-t(R)C=N]Ti(CH3)CH2SiMe3 {R = (t)3u (7)} was prepared via alkylation of the corresponding methyl chloride derivative with BrMgCH2SiMe3. When treated with B(C6F5)(3), compounds 1b-6b are rapidly converted into the ion pairs {Cp[Bu-t(R)C=N]TiCH3}(+)[H3C(B(C6F5)(3)](-), 1c-6c; mixed alkyl compound 7 yields the ion pair [Cp*((Bu2C)-Bu-t=N)TiCH2SiMe3](+)[H3C(B(C6F5)(3)](-), 7c, exclusively. Multinuclear NMR experiments show that ion pairing is tight in these compounds and that ketimide ligand rotation is occurring with a slightly higher barrier in comparison to the neutral derivatives b. Ion pairs 1c-5e undergo a decomposition process involving loss of methane and producing the neutral compounds Cp[Bu-t(R)C=N]Ti(C6F5)[CH2B(C6F5)(2)], 1d-5d. The X-ray crystal structure of Id has been determined. Active cationic compounds are not regenerated from neutral compounds d in the presence of B(C6F5)(3) and thus this reaction is a potential deactivation pathway for these particular ion pairs. Detailed kinetic studies on the decomposition of 2c show the reaction to be first order in [2c] with activation parameters of Delta H-double dagger = 20.6(8) kcal mol(-1) and Delta S-double dagger = -8.5(10) eu, corresponding to Delta G(298)(double dagger) of 23.1(8) kcal mol(-1). A substantial kinetic isotope effect of k(H)/k(D) = 9.1(6) was measured using d(6)-2c. Further mechanistic experiments, including crossover and examination of alkane elimination from mixed alkyl ion pair 7c, point to a sigma-bond metathesis mechanism for the production of compounds d. The implications of our results for other, related catalyst systems are discussed.

  DOI：

  10.1021/ja994378c