Ti(OtBu)[{(O-2,4-tBu2C6H2)-6-CH2}3N] | 851636-66-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Ti(OtBu)[{(O-2,4-tBu2C6H2)-6-CH2}3N]
• 英文别名: tris(2-oxy-3,5-di-tert-butylbenzyl)amino titanium(IV) tert-butoxide；Ti(O^tBu)[{(O-2,4-^tBu₂C₆H₂)-6-CH₂}₃N]；[nitrilotris(3,5-di-tert-butyl-2-cresolato)]Ti(O(t)Bu)；Ti(OtBu)(N(CH2C6H2-3,5-tBu2-2-O)3(3-))
• CAS: 851636-66-3
• 化学式: C₄₉H₇₅NO₄Ti
• 分子量: 790.019
• InChiKey: LIXHYSAYVUFGER-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 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：

  Ti(OtBu)[{(O-2,4-tBu2C6H2)-6-CH2}3N] 、 环庚三烯酚酮 以 苯 为溶剂， 以96%的产率得到[nitrilotris(3,5-di-tert-butyl-2-cresolato)](tropolonato)titanium(IV)
  参考文献：
  名称：

  Six-Coordinate Titanium Complexes of a Tripodal Aminetris(phenoxide) Ligand:  Synthesis, Structure, and Dynamics

  摘要：

  The five-coordinate titanium(IV) alkoxide LTi(O'Bu) (LH3 = tris(2-hydroxy-3,5-di-tert-butylbenzyl)amine) is protonolyzed readily by the conjugate acids of monoanionic bidentate ligands, both symmetrical (tropolone, acetylacetone, di-p-toluoylmethane) and unsymmetrical (8-hydroxyquinoline, salicylaldehyde, 2,6-diformyl-p-cresol, anthrarufin). The geometry of these complexes, which is pseudo-octahedral with the tripodal ligand adopting a chiral, propeller-like conformation, has been confirmed in four cases by X-ray crystallography. Variable-temperature NMR spectroscopy indicates that the six-coordinate complexes undergo two dynamic processes. First, the ligands undergo a twisting motion that results in racemization, a process which is over 10(4) times faster than in five-coordinate complexes. The rate acceleration upon binding of an equatorial ligand is ascribed to steric repulsions with one of the cis phenoxides; the dynamics of a binuclear dibenzyl phosphate-bridged compound, which has a unique conformation of the tripodal ligand, indicates that flexing the cis pheroxide is the rate-limiting step in racemization. Second, the complexes undergo a process that interchanges the inequivalent arms of the tripodal ligand, This process involves a trigonal twist that shifts the bidentate ligand between clefts in the tripod. The intermediate geometry in the reaction appears to be a transition state and not a long-lived intermediate, as judged from the relative rates of interconversion of tripod arms and chelate ends in the ditoluoylmethane complex, Tripod arm interchange takes place without partial dissociation of the bidentate chelate, a reaction that has been observed on a slower time scale in one case.

  DOI：

  10.1021/ic048403d
• 作为产物：
  描述：

  titanium(IV) tetrabutoxide 、 tris(4,6-di-tert-butyl-2-hydroxybenzyl)amine 以 not given 为溶剂， 以96%的产率得到Ti(OtBu)[{(O-2,4-tBu2C6H2)-6-CH2}3N]
  参考文献：
  名称：

  对三脚架钛醇盐的水解具有显着的热力学稳定性。

  摘要：

  单体氢氧化钛（IV）配合物LTi（OH）（LH（3）=三（2-羟基-3,5-二叔丁基苄基）胺）在空间上受抑制而缩合为mu-oxo二聚体对于甲醇钛在THF中的水解，K（eq）＝ 0.012不能通过醇盐的水解来制备。

  DOI：

  10.1039/b315092e

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
• 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
  作者：Kotohiro Nomura、Udomchai Tewasekson、Yuki Takii

  DOI：10.1021/acs.organomet.5b00303

  日期：2015.7.13

  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.