[Ti(N-4-C6H4Me)Cl2(pyridine)3] | 172481-12-8

• 英文名称: [Ti(N-4-C6H4Me)Cl2(pyridine)3]
• 英文别名: [Ti(N-p-tolyl)Cl2(py)3]
• CAS: 172481-12-8
• 化学式: C₂₂H₂₂Cl₂N₄Ti
• 分子量: 461.229
• InChiKey: QWAJNVOMXGMEJY-UHFFFAOYSA-L

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：
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反应信息

• 作为反应物：
  描述：

  1,3-二甲基吲哚 、 [Ti(N-4-C6H4Me)Cl2(pyridine)3] 在 正丁基锂 作用下， 以 甲苯 、 四氢呋喃 为溶剂， 以70%的产率得到
  参考文献：
  名称：

  Generation of Ti^II Alkyne Trimerization Catalysts in the Absence of Strong Metal Reductants

  摘要：

  Low-valent Ti-II species have typically been synthesized by the reaction of Ti-IV halides with strong metal reductants. Herein we report that Ti-II species can be generated simply by reacting Ti-IV imido complexes with 2 equiv of alkyne, yielding a metallacycle that can reductively eliminate pyrrole while liberating Ti-II. In order to probe the generality of this process, Ti-II-catalyzed alkyne trimerization reactions were carried out with a diverse range of Ti-IV precatalysts.

  DOI：

  10.1021/acs.organomet.7b00096
• 作为产物：
  描述：

  乙烷,三氯氟- 、 trans,mer-[Ti(t-butylimide)Cl2(pyridine)3] 以 二氯甲烷 为溶剂， 以42%的产率得到[Ti(N-4-C6H4Me)Cl2(pyridine)3]
  参考文献：
  名称：

  Synthesis and imido-group exchange reactions of tert-butylimidotitanium complexes

  摘要：

  用 Bu t NH 2（6 个当量）处理 TiCl 4，然后加入 bpy（2 个当量，4-叔丁基吡啶）或吡啶 (py)（2 或 4 个当量），可分别得到五或六配位叔丁基亚氨基配合物 [Ti(NBu t )Cl 2 (bpy) 2 ]或 [Ti(NBu t )Cl 2 (py) n ]（n = 2 或 3*），产率良好。 将 [Ti(NBu t )Cl 2 (py) 3 ] 与 RNH 2 反应，可得到相应的芳基亚甲基衍生物 [Ti(NR)Cl 2 (py) 3 ]（R = Ph、* C 6 H 4 Me-4、* C 6 H 4 NO 2 -4、* C 6 H 3 Me 2 -2,6 或 C 6 H 3 Pr i 2 -2,6）。在[Ti(NBu t )Cl 2 (py) n ]（n 分别为 2 或 3）中加入 tmen 或 pmdien，可得到相应的二齿或三齿胺配合物、 [Ti(NBu t )Cl 2 (tmen)] 或 [Ti(NBu t )Cl 2 (pmdien)]* （tmen = Me 2 NCH 2 CH 2 NMe 2，pmdien = N,N,N′,N″,N″-五甲基二乙烯三胺）。标有 * 的络合物已通过晶体学鉴定。

  DOI：

  10.1039/a607735h
• 作为试剂：
  描述：

  1-己炔 、 二(4-甲基苯基)二氮烯 在 [Ti(N-4-C6H4Me)Cl2(pyridine)3] 作用下， 反应 16.0h， 生成 2,5-di-n-butyl-1-tolyl-1H-pyrrole 、 2,4-di-n-butyl-1-(p-tolyl)-1H-pyrrole
  参考文献：
  名称：

  Generation of Ti^II Alkyne Trimerization Catalysts in the Absence of Strong Metal Reductants

  摘要：

  Low-valent Ti-II species have typically been synthesized by the reaction of Ti-IV halides with strong metal reductants. Herein we report that Ti-II species can be generated simply by reacting Ti-IV imido complexes with 2 equiv of alkyne, yielding a metallacycle that can reductively eliminate pyrrole while liberating Ti-II. In order to probe the generality of this process, Ti-II-catalyzed alkyne trimerization reactions were carried out with a diverse range of Ti-IV precatalysts.

  DOI：

  10.1021/acs.organomet.7b00096

文献信息

• Transition metal imide/organic imine metathesis reactions: unexpected observations
  作者：Jacqueline M. McInnes

  DOI：10.1039/a803719a

  日期：——

  Mixtures of [Ti(NBut)Cl2(py)3] 1 and PhC(NAr)H (Ar = C6H3Me2-2,6 or C6H4Me-4) gave quantitative conversion to [Ti(NAr)Cl2(py)3] and PhC(NBut)H, the products of TiNBut/CNAr transition metal imide/organic imine meta-thesis; examination of the kinetics for Ar = C6H4Me-4 showed that the rate limiting step for this process is zero order in [1], demonstrating that these reactions do not involve metal imide particiption in the rate limiting step.

  将[T i(NBut)Cl2(py)3] 1与PhC(NAr)H（Ar = C6H3Me2-2,6或C6H4Me-4）的混合物反应，定量转化为[T i(NAr)Cl2(py)3]和PhC(NBut)H，这些是TiNBut/CNAr过渡金属亚胺/有机亚胺的元反应产物；对Ar = C6H4Me-4的动力学研究表明，该过程的速率限制步骤在[1]中是零阶，证明这些反应的速率限制步骤不涉及金属亚胺的参与。
• Titanium and niobium imido complexes stabilized by heteroscorpionate ligands
  作者：A. Otero、J. Fernández-Baeza、A. Antiñolo、J. Tejeda、A. Lara-Sánchez、L. Sánchez-Barba、A. M. Rodríguez

  DOI：10.1039/b411113c

  日期：——

  The reaction of [Ti(NR)Cl2(py)3] (R = tBu, p-tolyl, 2,6-C6H3iPr2) with [Li(bdmpza)(H2O)}4] [bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate] and [Li(bdmpzdta)(H2O)}4] [bdmpzdta = bis(3,5-dimethylpyrazol-1-yl)dithioacetate] affords the corresponding complexes [Ti(NR)Cl(κ3-bdmpzx)(py)] (x = a, R = tBu 1, p-tolyl 2, 2,6-C6H3iPr23; x = dta, R = tBu 4, p-tolyl 5, 2,6-C6H3iPr26), which are the first examples of imido Group 4 complexes stabilized by heteroscorpionate ligands. The solid-state X-ray crystal structure of 1 has been determined. The titanium centre is six-coordinate with three fac-sites occupied by the heteroscorpionate ligand and the remainder of the coordination sphere being completed by chloride, imido and pyridine ligands. The complexes 1–6 are fluxional at room temperature. The pyridine ortho- and meta-proton resonances show evidence of dynamic behaviour for this ligand and variable-temperature NMR studies were carried out in order to study their dynamic behaviour in solution. The complexes [Nb(NR)Cl3(py)2] (R = tBu, p-tolyl, 2,6-C6H3iPr2) reacted with [Li(bdmpza)(H2O)}4] and (Hbdmpze) [bdmpze = 2,2-bis(3,5-dimethylpyrazol-1-yl)ethoxide], the latter with prior addition of nBuLi, to give the complexes [Nb(NR)Cl2(κ3-bdmpzx)] (x = a, R = tBu 7, p-tolyl 8, 2,6-C6H3iPr29; x = e, R = tBu 10, p-tolyl 11, 2,6-C6H3iPr212) and these are the first examples of imido Group 5 complexes with heteroscorpionate ligands. The structures of these complexes have been determined by spectroscopic methods.

  准备好的反应物，前者则没有。
• New titanium imido complexes containing piperazine-based diamido–diamine ligands
  作者：Julian Lloyd、Sergei Z. Vatsadze、David A. Robson、Alexander J. Blake、Philip Mountford

  DOI：10.1016/s0022-328x(99)00447-7

  日期：1999.12

  Syntheses of the new piperazine derivatives 1,4-bis(2-amino-4-tert-butylbenzyl)piperazine (2) and 1,4-bis(2-trimethylsilylamino-4-R-benzyl)piperazine (R = H 3 or Bu' 4; H2L1 and H2L1 respectively) are described along with the X-ray crystal structure of 2. Treatment of H2L1 and H2L1 with n-butyl lithium gives the amido derivatives Li2L1 (5) and Li2L2 (6), which react with [Ti(NBu')Cl-2(py)(3)] to form [Ti(NBu')(L-1)] (7) and [Ti(NBu')(L-2)] (8). Reaction of Li2L1 with [Ti(N-4-C6H4Me)Cl-2(py)(3)] gives the corresponding arylimido homologue [Ti(N-4-C6H4Me)(L-1)] (9). The X-ray structure of 8 shows a strongly transoid disposition of the aryl rings of the L-1 ligand and this geometry is maintained in solution. Somewhat surprisingly 7 does not undergo tert-butylimide/arylamine exchange with 4-methylphenylamine to form 9. The related compound N,N'-bis(2-trimethylsilylaminobenzyl)-N,N'-dimethyl-1,3-diaminopropane (12, H2L3) and its lithium salt Li2L3 (13) are also described. However, reaction of 13 with [Ti(NBu')Cl-2(py)(3)] affords no tractable product. (C) 1999 Elsevier Science S.A. All rights reserved.
• Dalton communications. Exchange of organoimido groups at a mononuclear titanium centre and a crystallographic evaluation of the relative structural influences of the NBut, NC6H4Me-4 and NC6H4NO2-4 ligands
  作者：Philip E. Collier、Simon C. Dunn、Philip Mountford、Oleg V. Shishkin、Daniel Swallow

  DOI：10.1039/dt9950003743

  日期：——

  The tert-butylimido complex [Ti(NBu(t))Cl-2(py)(3)] 1a (py = pyridine) undergoes exchange reactions of the NBu(t) ligand with arylamines RNH(2) to form the arylimido derivatives [Ti(NR)Cl-2(py)(3)] (R = C(6)H(4)Me-4 1b, C6H4NO2-4 1c or C(6)H(3)Me(2)-2,6 1d); comparison of the crystal structures of 1a-1c gave a direct evaluation of N-substituent effects in d(0), six-co-ordinated organoimido complexes.