[TiCl(tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine(-3H))] | 905435-86-1

• 英文名称: [TiCl(tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine(-3H))]
• 英文别名: TiCl[{(O-2,4-^tBu₂C₆H₂)-6-CH₂}₃N]；TiCl(N(CH2C6H2-3,5-tBu2-2-O)3(3-))
• CAS: 905435-86-1
• 化学式: C₄₅H₆₆ClNO₃Ti
• 分子量: 752.357
• InChiKey: MGJLBGWILUMKNU-UHFFFAOYSA-J

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：

  [TiCl(tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine(-3H))] 、 双(三甲基硅烷基)氨基钾 以 乙醚 为溶剂， 反应 18.0h， 以81%的产率得到
  参考文献：
  名称：

  三（酚基）-胺配体负载的钛（IV）甲酸酯配合物

  摘要：

  摘要描述了由三（酚基）-胺配体稳定的钛（IV）末端和桥联甲酸络合物的合成。通过氯化物前体[（O3N）的盐复分解反应合成了末端甲酸络合物[（O3N）Ti（OCHO）]（H3（O3N）=三（4,6-二叔丁基-2-羟基苄基）胺） [TiCl]与甲酸钠。末端甲酸酯与阳离子钛（IV）络合物[（O3N）Ti（Et2O）] [B（C6F5）4]的反应，该苄基络合物是[[O3N）Ti（CH2Ph）]与[PhMe2NH]的质子分解反应[B（C6F5）4]给出了桥联的甲酸络合物[{（O3N）Ti} 2（μ-OCHO-ηO：ηO'）] [B（C6F5）4]，其结构通过单晶X射线衍射表征。尝试通过KHMDS（HMDS = N（SiMe3）2）对甲酸配体进行质子化以产生CO2双阴离子失败，但导致了[[O3N）Ti {N（SiMe3）2}]的形成。

  DOI：

  10.1016/j.poly.2018.11.025
• 作为产物：
  描述：

  titanium(IV) chloride tetrahydrofuran 、 tris(4,6-di-tert-butyl-2-hydroxybenzyl)amine 以 甲苯 为溶剂， 反应 6.0h， 以75%的产率得到[TiCl(tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine(-3H))]
  参考文献：
  名称：

  Synthesis of Titanium Complexes Containing an Amine Triphenolate Ligand of the Type [TiX{(O-2,4-R₂C₆H₂)-6-CH₂}₃N] and the Ti–Al Heterobimetallic Complexes with AlMe₃: Effect of a Terminal Donor Ligand in Ethylene Polymerization

  摘要：

  The synthesis of various titanatranes containing tris(aryloxo)amine ligands, TiX[{(O-2,4-R2C6H2)-6-CH2}(3)N] [R = Me (1), Bu-t (2); X = (OPr)-Pr-i (a), (OBu)-Bu-t (b), OCH(CF3)(2) (c), OC(CF3)(3) (d), Cl (e)], and some reactions with Al alkyls have been explored. The Ti-Al heterobimetallic complexes [TiMe{(O-2,4-Me2C6H2-6-CH2)(2)(mu(2)-O-2,4-Me-2-C6H2-6-CH2)}N-[NMe2Al(mu(2)-OR')] [R' = Bu-t (3b), CH-(CF3)(2) (3c), C(CF3)(3) (3d)] were isolated by reaction of 1b-d with 1 equiv of AlMe3, whereas reaction of 2b with AlMe3 in toluene did not take place under the same conditions and the reaction of 2c afforded the methyl complex TiMe[{(O-2,4-(Bu2C6H2)-Bu-t)-6-CH2}(3)N]. Structures of 3b,c were determined by X-ray crystallography. These complexes exhibited high catalytic activities for ethylene polymerization in n-octane in the presence of MAO, and the activity by 1 and 2 was affected by the terminal donor ligand (X) as well as the substituent on the atrane ligand (R). The activities by 1c,d increased upon addition of AlMe3, and the corresponding heterobimetallic complexes (3c,d) showed high activities, whereas an increase in the activity upon addition of AlMe3 was not observed by 1b,e, and 2c,e.

  DOI：

  10.1021/acs.organomet.5b00303

文献信息

• Redox-Active Tripodal Aminetris(aryloxide) Complexes of Titanium(IV)
  作者：Davide Lionetti、Andrew J. Medvecz、Vesela Ugrinova、Mauricio Quiroz-Guzman、Bruce C. Noll、Seth N. Brown

  DOI：10.1021/ic100347h

  日期：2010.5.17

  dianisylamino-substituted compound lacking the tert-butyl group ortho to the phenol (H,An2NLH3) is also readily prepared. The ligands are metalated by titanium(IV) tert-butoxide to form the five-coordinate alkoxides LTi(OtBu). Treatment of the tert-butoxides with aqueous HCl yields the five-coordinate chlorides LTiCl, and with acetylacetone gives the six-coordinate diketonates LTi(acac). The diketonate

  由曼尼希（Mannich）制备具有相对电子富集的酚的新的空间受限的三脚架胺三（芳氧基）配体N（CH 2 C 6 H 2 -3- t Bu-5-X-2-OH）3（t Bu，X LH 3）缩合（X = OCH 3）或通过苄基保护的溴水杨醛上的还原胺化/ Hartwig-Buchwald胺化序列（X = N [C 6 H 4 - p -OCH 3 ] 2），然后使用Pearlman's催化剂（Pd （OH）2 / C）。缺乏的类似dianisylamino取代的化合物叔酚（H，An 2 N LH 3）邻位的丁基也很容易制备。所述配体被叔丁醇钛（IV）金属化以形成五配位醇盐LTi（O t Bu）。用盐酸水溶液处理叔丁醇盐可得到五配位的氯化物LTiCl，而用乙酰丙酮则可得到六配位的二酮酸酯LTi（acac）。二酮酸酯配合物t Bu，X LTi（acac）显示出可逆的基于配体的氧化，其中X = t Bu，MeO和An
• Fixation of Dinitrogen at an Asymmetric Binuclear Titanium Complex
  作者：Dae Young Bae、Gunhee Lee、Eunsung Lee

  DOI：10.1021/acs.inorgchem.1c01050

  日期：2021.9.6

  The titanium complex successfully generates ammonia in the presence of an excess amount of PCy3HI and KC8 in 154% yield (per titanium atom). A titanium complex with a bulkier TPA does not form a dinitrogen complex, and mononuclear titanium dinitrogen complexes were not accessible, presumably because of the high tendency of early transition metals to form binuclear dinitrogen complexes.

  报道了一种由三酚胺 (TPA) 配体支持的新型二钛二氮配合物。通过单晶 X 射线衍射和拉曼和核磁共振光谱分析揭示了两个钛中心的不同配位几何结构。因此，TPA 和氮配体的配位导致三角双锥几何结构，而八面体钛中心是在乙醚溶剂分子中 C-O 键断裂产生的乙醇盐的额外配位后获得的。在过量的 PCy 3 HI 和 KC 8存在下，钛络合物成功生成氨产率为 154%（每个钛原子）。具有较大 TPA 的钛络合物不会形成二氮络合物，并且无法获得单核钛二氮络合物，大概是因为早期过渡金属形成双核二氮络合物的高趋势。
• Molecular engineering of coordination pockets in chloro-tris-phenoxo complexes of titanium(IV)
  作者：Alastair J. Nielson、Chaohong Shen、Joyce M. Waters

  DOI：10.1016/j.poly.2005.12.027

  日期：2006.7

  The chloro-tris-phenoxo complexes [TiCl(OAr)(3)] (OAr = OC6H4CMe-(3)-4 (1). OC6H2Me3-2A (2). OC6H2Me3-2,4,6 (4), OC6H3(CHMe2)(2)-2,6 (5), OC6H3(CMe3)(2)-2,4 (6) and OC6H4Ph-2 (8) are prepared by heating 3 equivalents of the phenol and [TiCl4] in toluene. X-ray crystal structure determinations show that 2 is a phenoxy-bridged dimer with the ortho-methyl groups making the beginning of a pocket about the terminal chloro ligand and 6 is a tetrahedral monomer in which the pocket is more well developed by the ortho-tert-butyl groups. Both 2 and 6 react with dmbipy to give [TiCl(OAr)(3)(dmbipy)] [OAr = OC6H3Me2-2,4 (3) and OC6H3(CMe3)2-2,4 (7)] in which the original pocket is destroyed. Reaction of TiCl4 with 3 equivalents of LiOC6H4Ph-2 in diethyl ether gives [TiCl(OC6H4Ph-2)(3)(diethyl ether)] (9) for which an X-ray crystal structure determination shows a trigonal bipyramidal coordination geometry with the diethyl ether lying trans to the chloro ligand. The three phenoxide ligands make up the equatorial plane which takes the 2-phenyl substituent on each phenoxo ligand away from the chloro ligand resulting in a partially collapsed cavity. The tied-back analogues of 2 and 6, [TiClOC6H2Me2-2,4-CH2-6)(3)N)] (11) and [TiCl(OC6H2(CMe3)(2)-2,4-CH2-6}(3)N)] (.) diethyl ether (12), are prepared by adding (HOArCH2)(3)N [Ar = C6HMe2-2,4 and C6H2(CMe3)(2) 2.4] to [TiCl(OCHMe2)(3)] in diethyl ether. An X-ray crystal structure of 12 showed a trigonal bipyramidal structure with a coordination environment about the terminal chloro ligand similar to that found in 6. Complex 12 reacts with pyridine to form the 6-coordinate complex [TiClOC6H2(CMe3)(2)-2,4-CH2-6)(3)N)(py)] (13). (c) 2006 Elsevier Ltd. All rights reserved.
• Effect of Terminal Aryloxo Ligands in Ethylene Polymerization Using Titanatranes of the Type, [Ti(OAr){(O-2,4-R₂C₆H₂)-6-CH₂}₃N]: Synthesis and Structural Analysis of the Heterobimetallic Complexes of Titanatranes with AlMe₃
  作者：Yuki Takii、Prabhuodeyara M. Gurubasavaraj、Shohei Katao、Kotohiro Nomura

  DOI：10.1021/om3008635

  日期：2012.12.10

  Effects of aryloxo terminal ligands and AlMe3 in ethylene polymerization using a series of Ti(OAr)[(O-2,4-R2C6H2)-6-CH2}(3)N] [R = Me (1), Bu-t (2); Ar = 2,6-Me2C6H3 (a), 2,6-(Pr2C6H3)-Pr-i (b), 2,6-Ph2C6H3 (c), 2,6-F2C6H3 (d), C6F5 (e)] (1a-1e, 2d,2e) in the presence of methylaluminoxane (MAO) have been explored. Reactions of 1b,1d,1e, which showed an increase in the activity upon addition of a small amount of AlMe3, with 1.0 equiv of AlMe3 afforded heterobimetallic Ti-Al complexes, TiMe(O-2,6-(Pr2C6H3)-Pr-i) [(O-2,4-Me2C6H2-6-CH2)(mu(2)-O-2,4-Me2C6H2-6-CH2)(Me2Al-mu(2)-O-2,4-Me2C6H2-6-CH2)N] (3b) and [TiMe(O-2,4-Me2C6H2-6-CH2)(2)(mu(2)-O-2,4-Me2C6H2-6-CH2)N}][Me2Al(mu(2)-OAr)] [Ar = 2,6-F2C6H3 (3d), C6F5 (3e)], in moderate yields, and their structures were determined by X-ray crystallography. In contrast, the similar reaction of la (which showed a decrease in the activity upon addition of AlMe3) yielded [Al(mu(2)-O-2,6-C6H3)Me-2](2) and TiMe[(O-2,4-Me2C6H2)-6-CH2}(3)N] as isolated forms: [Al(mu(2)-OC6F5)Me-2](2) was isolated from the mixture in the reactions of 1c,2d,2e. The isolated heterobimetallic complexes (3b,3d,3e) exhibited high catalytic activities for ethylene polymerization in the presence of MAO, suggesting that these bimetallic species play a role in this catalysis.