tetra(isopropoxy)hafnium isopropanol | 1070655-38-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tetra(isopropoxy)hafnium isopropanol
• 英文别名: [Hf(OiPr)₄(iPrOH)]；Hf(OiPr)4(HOiPr)；[Hf(OiPr)4(iPrOH)]；Hafnium(4+);propan-2-ol;propan-2-olate
• CAS: 1070655-38-7
• 化学式: C₁₅H₃₆HfO₅
• 分子量: 474.938
• InChiKey: GTKHNOIDTQESEF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.59
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  113
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tetra(isopropoxy)hafnium isopropanol 、 2,4-Ditert-butyl-6-[[tert-butyl-[(3,5-ditert-butyl-2-hydroxyphenyl)methyl]amino]methyl]phenol 以 甲苯 为溶剂， 反应 16.0h， 以48%的产率得到2,4-Ditert-butyl-6-[[tert-butyl-[(3,5-ditert-butyl-2-oxidophenyl)methyl]amino]methyl]phenolate;2,4-ditert-butyl-6-(propan-2-yloxymethyl)phenolate;hafnium(4+);propan-2-olate
  参考文献：
  名称：

  Zirconium and Hafnium Complexes Containing N-Alkyl-Substituted Amine Biphenolate Ligands: Unexpected Ligand Degradation and Divergent Complex Constitutions Governed by N-Alkyls

  摘要：

  The reactivity and thermal stability of zirconium and hafnium complexes containing the N-alkyl-substituted amine biphenolate ligands of the type [RN(CH2-2-O-3,5-C6H2(tBu)(2))(2)](2-) ([R-ONO](2-); R = tBu (1a), iPr (1b), or nPr (1c)) were investigated. The reactions of either [1a]M(OiPr)(2) (M = Zr or Hf) with equimolar H-2[1a] or M(OiPr)(4)(HOiPr) (M = Zr or Hf) with 2 equiv of H-2[1a] at 25 degrees C in diethyl ether or 80 degrees C in toluene afford moderate yields of colorless crystals of M[1a](OiPr)-(iPrOCH(2)-2-O-3,5-C6H2(tBu)(2)) (M = Zr (4a) or Hf (5a)). Controlled experiments revealed that the Production of 4a and 5a proceeds via unexpected thermal degradation of H-2[1a] that produces a highly reactive, transient ortho-quinone methide intermediate. Similar reactions employing H-2[1b] and H-2[1c], however, led to the formation of homoleptic bis-ligand complexes Zr[1b](2) (8b) and M[1c](2) (M = Zr (8c) or Hf (9c)) as colorless crystals. Decisive factors governing these divergent reaction pathways and complex constitutions are discussed. The X-ray structures of 4a, 5a, 8b, 8c, and 9c are presented.

  DOI：

  10.1021/ic400891b
• 作为产物：
  描述：

  异丙醇 生成 tetra(isopropoxy)hafnium isopropanol
  参考文献：
  名称：

  VERMA, V.;KHER, S.;KAPOOR, R. N., ACTA CHIM. HUNG., 1984, 115, N 1, 21-25

  摘要：

  DOI：

文献信息

• Alternating Sequence Controlled Copolymer Synthesis of α-Hydroxy Acids via Syndioselective Ring-Opening Polymerization of <i>O</i>-Carboxyanhydrides Using Zirconium/Hafnium Alkoxide Initiators
  作者：Yangyang Sun、Zhaowei Jia、Changjuan Chen、Yong Cong、Xiaoyang Mao、Jincai Wu

  DOI：10.1021/jacs.7b04712

  日期：2017.8.9

  challenges until now for lack of suitable catalysts/initiators. In this work, a highly syndioselective ROP of OCAs system as the first stereoselective example in this area is reported using zirconium/hafnium alkoxides as initiators with the highest Pr value up to 0.95. Furthermore, these initiators were successfully applied in the precisely alternating sequence controlled copolymerization of PheOCA and

  O-羧酸酐（OCA）的开环聚合（ROP）由于易于修饰OCA的侧基，可以得到具有不同官能团的多种聚（α-羟基酸）（PAHAs），这可以扩展PAHAs的应用广泛。由于缺乏合适的催化剂/引发剂，O-羧酸酐的立体选择性聚合和OCA的进一步顺序控制交替共聚仍然是一个巨大的挑战。在这项工作中，报道了使用锆/铪醇盐作为引发剂的 OCA 系统的高度间选择性 ROP 作为该领域的第一个立体选择性例子，最高 Pr 值高达 0.95。此外，这些引发剂已成功应用于 PheOCA 和 Tyr(Bn)OCA 的精确交替顺序控制共聚，
• Oxo-Bridged Bimetallic Group 4 Complexes Bearing Amine-Bis(benzotriazole phenolate) Derivatives as Bifunctional Catalysts for Ring-Opening Polymerization of Lactide and Copolymerization of Carbon Dioxide with Cyclohexene Oxide
  作者：Ching-Kai Su、Hui-Ju Chuang、Chen-Yu Li、Chun-Yue Yu、Bao-Tsan Ko、Jhy-Der Chen、Ming-Jen Chen

  DOI：10.1021/om500784a

  日期：2014.12.22

  report the synthesis, crystal structure, and catalytic studies for ring-opening polymerization (ROP) of group 4 metal alkoxides based on amine-BiBTP derivatives (amine-BiBTP = amine-bis(benzotriazole phenolate)). Dinuclear group 4 metal alkoxides [(amine-BiBTP)Mt(OiPr)}2(μ-O)] (4–7, Mt = Ti, Zr, Hf) resulted from treatment of amine-BiBTP-H2 as the ligand precursor with 1.0 molar equiv of metal precursor

  我们报告的合成，晶体结构，和基于胺-BiBTP衍生物（胺-BiBTP =胺-双（苯并三唑酚盐））的第4组金属醇盐的开环聚合（ROP）的催化研究。双核第4组金属醇盐[（（amine-BiBTP）M t（O i Pr）} 2（μ-O）]（4 – 7，M t = Ti，Zr，Hf）是由于胺-BiBTP-H的处理而产生的2作为配体前体，具有1.0摩尔当量的金属前体（Ti（O i Pr）4，Zr（O i Pr）4（i PrOH）或Hf（O i Pr）4（i（PrOH）），然后以高收率加入H 2 O（0.5当量）。的固态结构4 - 7揭示了双金属BiBTP结扎金属（IV）醇盐与氧代配位体螯合2个金属原子和金属-O（μ-氧代）的键合方式-金属部分呈直线型。系统地研究了氧桥联双金属配合物的丙交酯聚合反应和二氧化碳/环己烯氧化物的共聚反应。烷氧基锆6以“活”和“永生”的方式在丙交酯的ROP中显示出有效的催
• Titanium, zirconium and hafnium complexes bearing amino-benzotriazole phenolate ligands as efficient catalysts for ring-opening polymerization of lactides
  作者：Chia-Jung Yu、Chen-Yu Li、Chen-Yen Tsai、Bao-Tsan Ko

  DOI：10.1016/j.inoche.2019.107561

  日期：2019.11

  hyl)phenolate ligand (C1MOBTP) were synthesized and structurally characterized. The reaction of Ti(OiPr)4 or M(OiPr)4(iPrOH) (M = Zr, Hf) with C1MOBTP-H (2.0 M equiv.) in toluene produced the hexa-coordinated bis-adduct metal complex [(C1MOBTP)2M(OiPr)2] (M = Ti for 1, Zr for 2 and Hf for 3). Experimental results indicate that hafnium complex 3 displayed the higher catalytic activity than those of

  摘要 合成了 2-(2H-苯并三唑-2-基)-4-甲基-6-(吗啉甲基)苯酚配体 (C1MOBTP) 中的第 4 族催化剂并对其进行了结构表征。Ti(OiPr)4 或 M(OiPr)4(iPrOH)（M = Zr，Hf）与 C1MOBTP-H（2.0 M 当量）在甲苯中反应生成六配位双加合物金属络合物 [(C1MOBTP) 2M(OiPr)2]（M = Ti 用于 1，Zr 用于 2，Hf 用于 3）。实验结果表明，铪配合物 3 对受控 L-LA 聚合显示出比具有二-C1MOBTP 特征的配合物 1 和 2 更高的催化活性。铪醇盐 3 不仅以“受控”的方式有效地催化开环聚合，而且以“永生”的方式有效地催化开环聚合，从而得到具有预期分子量和窄分子量分布的相应聚合物。
• Benzotriazole Phenoxide Hafnium Complexes as Efficient Catalysts for the Ring‐Opening Polymerization of Lactide: Synthesis, Characterization, and Kinetics of Polymerization Catalysis
  作者：Hui‐Ju Chuang、Ban‐Hsin Wu、Chen‐Yu Li、Bao‐Tsan Ko

  DOI：10.1002/ejic.201301422

  日期：2014.3

  at 30 °C gave the hafnium tetra-adduct [(C8BTP)4Hf] (5). Single-site hafnium 4 proved to be an active catalyst in the polymerization of lactide (LA) in solution with “living” and “immortal” characteristics, producing polymers with the expected molecular weights and narrow molecular weight distributions (PDI ≤ 1.30). BTP-containing Hf complex 5 efficiently catalyzed the polymerization in a controlled

  已经合成了带有双或四 BTP 配体（BTP = N,O-二齿苯并三唑酚盐）的铪配合物并对其进行了结构表征。[Hf(OiPr)4(iPrOH)] 与 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (CMe2PhBTP-H), 2-( 2H-苯并三唑-2-基)-4,6-二叔丁基苯酚 (tBuBTP-H) 和 2-叔丁基-6-(5-氯-2H-苯并三唑-2-基)-4-甲基苯酚(TMClBTP-H) (2.0 mol-equiv.) 在 30 °C 的己烷中得到单体铪络合物 [(CMe2PhBTP)2Hf(OiPr)2] (1), [(tBuBTP)2Hf(OiPr)2] (2) , 和 [(TMClBTP)2Hf(OiPr)2] (3)。双加合物铪类似物 [(C8BTP)2Hf(OiPr)2] (4) 是通过类似处理空间上体积较小的
• Zirconium and hafnium complexes containing N-alkyl substituted amine biphenolate ligands: coordination chemistry and living ring-opening polymerization catalysis
  作者：Lan-Chang Liang、Sheng-Ta Lin、Chia-Cheng Chien、Ming-Tsz Chen

  DOI：10.1039/c3dt50152c

  日期：——

  The coordination chemistry of zirconium and hafnium complexes containing the tridentate amine biphenolate ligands [RN(CH2-2-O-3,5-C6H2(tBu)2)2]2− ([R-ONO]2−; R = tBu (1a), iPr (1b), nPr (1c)) featuring distinct N-alkyl substituents is described. Alcoholysis of Zr(OiPr)4(HOiPr) or Hf(OiPr)4(HOiPr) with H2[1a] in diethyl ether solutions at −35 °C generates the corresponding five-coordinate [1a]M(OiPr)2

  含有三齿胺双酚盐配体[RN（CH 2 -2-O-3,5-C 6 H 2（t Bu）2）2 ] 2−（[R-ONO] 2−的锆和ha配合物的配位化学； R ＝t Bu（1a），iPr（1b），n Pr（1c））具有不同的N-烷基取代基。Zr（OiPr）4（HOiPr）或Hf（OiPr）4（HOiPr）与H 2的醇解[ 1a]在-35°C的乙醚溶液中生成相应的五坐标[ 1a ] M（OiPr）2（M = Zr（2a），Hf（3a）），具有很高的分离产率。使用H 2 [ 1b ]的类似反应可生成六坐标的[ 1b ] M（OiPr）2（HOiPr）（M = Zr（2b ·HOiPr），Hf（3b ·HOiPr））作为异丙醇加合物。2b ·HOiPr和3b ·HOiPr的重复研磨乙醚分别给出五坐标2b和3b。在类似条件下用H 2 [ 1c ]处理M（OiPr）4（HOiPr），得到六坐标的[ 1c ]