[CrCl3(THF)3]

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: [CrCl3(THF)3]
• 化学式: 3C₄H₈O*3Cl*Cr
• 分子量: 374.676
• InChiKey: JGWROPSUDGINLB-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -2.2
• 重原子数：
  7.0
• 可旋转键数：
  0.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  [CrCl3(THF)3] 、 neptunyl(V) chloride 以 四氢呋喃 、 1,4-二氧六环 、 水 、 乙腈 为溶剂， 生成
  参考文献：
  名称：

  水/极性有机混合溶剂介质中的五价 Neptunyl ([O≡Np≡O]+) 阳离子-阳离子相互作用

  摘要：

  多价阳离子和含氧阴离子之间的键合相互作用是众所周知的，其特征在于溶液相配位化学中可预测的有利吉布斯能量。相比之下，通常预期相同电荷离子之间的相互作用是排斥的，并且受到阳离子溶剂化的强烈影响。这种本能规则的一个例外是存在由五价锕基阳离子 ([O≡An≡O]+) 与选定的多价阳离子相互作用产生的复合物。自 1960 年代以来，人们就知道这种阳离子 - 阳离子复合物存在，当时它们是由 Sullivan 和同事首次报道的。由五价线性二氧炔基阳离子供体和六价炔基或三价/四价金属阳离子受体之间的键合相互作用产生的弱锕基阳离子-阳离子复合物，最常见于水活性降低的介质，主要是高盐水性介质。五价锕系元素的这种相互作用与正在进行的研究相关，这些研究侧重于基于镅的上氧化态的先进核燃料加工系统。本研究的重点是探索选定的高电荷金属阳离子（Al3+、Sc3+、Cr3+、Fe3+、In3+ 和 $$ {\text{UO}}_{2}^{2

  DOI：

  10.1007/s10953-017-0647-2
• 作为试剂：
  描述：

  D-葡萄糖 在 [CrCl3(THF)3] 、 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene*HCl 、 氯化 1-乙基-3-甲基咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 以61%的产率得到5-hydroxymethyl-2-furfuraldehyde
  参考文献：
  名称：

  Role of N-heterocyclic carbenes in glucose conversion into HMF by Cr catalysts in ionic liquids

  摘要：

  As N-heterocyclic carbenes (NHCs) can be readily formed from deprotonation of their precursors-imidazolium salts (i.e., ionic liquids, ILs) that are typically used as solvent in homogenous glucose-to-5-hydroxymethylfurfural (HMF) conversion systems with CrClx (x = 2 or 3) as catalyst-the hypothesis that the (NHC)-CrClx complex is the true catalyst for such conversion exists in the literature, but it has not been tested. Reported herein are three sets of mechanistic probes to address the role of the NHC ligand in the glucose-to-HMF conversion by CrClx in ILs. Specifically, controls with all additives (reagents) involved in the conversion system, performances of in situ generated NHC ligands or Cr complexes as well as discrete NHC ligands and Cr complexes that were proposed to be the true catalyst, and quantitative NHC titration (poisoning) experiments conclusively show that the NHC ligand actually serves as a poison to the chromium catalyst system and that a superstoichiometric amount (2 or 3 equiv.) of the NHC ligand can completely shut down the catalysis. (c) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.apcata.2013.04.015

文献信息

• New main-group and early transition-metal complexes of mono-pendant arm triazacyclononane ligands
  作者：Sergei Y. Bylikin、David A. Robson、Nigel A. H. Male、Leigh H. Rees、Philip Mountford、Martin Schröder

  DOI：10.1039/b008267h

  日期：——

  KLc2a–c by reaction with potassium hydride in tetrahydrofuran (THF). An improved synthesis of HLc1c is also reported. Reaction of KLa–c with Group 13 metal salts MCl3 (M = Al, Ga or In) gives monomeric derivatives [M(κ4-La–c)Cl2] 3–5 in good yields. The crystal structure of [In(κ4-Lb)Cl2] 5b has been determined and confirms the six-coordinate, cis-dichloride structures proposed for these complexes. Reaction

  先前描述的单阴离子，侧链大环的新的3族，13族和早期过渡金属配合物的族 配体描述了L a，L b和L c，其中HL a  =（3,5-二甲基-2-羟基苄基）-4,7-二异丙基-1,4,7-三氮杂环壬烷1a，HL b  =（3,5-di -叔丁基-2-羟基苄基）-4,7-二异丙基-1,4,7-三氮杂环壬烷1b，且HL c  =（3,5-二叔丁基-2-羟基苄基）-4,7-二甲基-1,4,7-三氮杂环壬烷1c。这配体先兆1a–c被定量转换为相应的新钾盐KL a，KL b和KL c 2a–c通过与氢化钾 在 四氢呋喃（THF ）。还报道了HL c 1c的改进的合成。KL的反应A-C与第13族金属的盐的MC1 3（M =铝，Ga或In）给出的单体的衍生物[M（κ 4 -L A-C ）氯2 ] 3 - 5以良好的收率。[在（κ的晶体结构4 -L b）氯2 ]图5b已被确定和证实的六配位，顺提出用于这些
• Discovery and Optimization of New Chromium Catalysts for Ethylene Oligomerization and Polymerization Aided by High-Throughput Screening
  作者：David J. Jones、Vernon C. Gibson、Simon M. Green、Peter J. Maddox、Andrew J. P. White、David J. Williams

  DOI：10.1021/ja0518171

  日期：2005.8.1

  (p-tolyl)CrCl2(thf)3, identified two new classes of highly active chromium based systems for the oligomerization and polymerization of ethylene, respectively. The polymerization system comprises bidentate ortho-substituted anthracenyl Schiff bases bearing small primary or secondary alkyl imine substituents. The oligomerization catalysts are based upon tridentate ortho-triptycenyl-substituted Schiff bases with pyridylmethyl

  205 个成员席夫碱水杨醛亚胺配体文库的高通量筛选 (HTS)，源自带有大量邻位取代基的水杨醛，即 9-蒽基、1,4,5,8-四甲基蒽基或三烯基，与 (p- tolyl)CrCl2(thf)3，确定了两类新的高活性铬基体系，分别用于乙烯的低聚和聚合。聚合体系包含带有小的伯或仲烷基亚胺取代基的二齿邻位取代的蒽基席夫碱。低聚催化剂基于具有吡啶基甲基或喹啉基取代基的三齿邻三烯基取代的席夫碱。验证测试证实聚合催化剂体系的聚合生产率高达 3000 gx mmol(-1)h(-1)bar(-1)，而低聚催化剂的生产率高达 10 000 gx mmol(-1)h(-1) ) 条 (-1)。关键催化剂前体已通过 X 射线晶体学表征。
• [EN] TRANSITION METAL COMPLEXES<br/>[FR] TRANSITION METAL COMPLEXES
  申请人：SHELL INT RESEARCH

  公开号：WO2005090371A1

  公开（公告）日：2005-09-29

  A transition metal complex which is a bis-arylimine pyridine MXn complex, comprising a bis-arylimine pyridine ligand having the formula (I), wherein R1-R5, R7-R9, R12 and R14 are each, independently, hydrogen, optionally substituted hydrocarbyl, an inert functional group, or any two of R1-R3 and R7-R9 vicinal to one another taken together may form a ring, and R6 is hydrogen, optionally substituted hydrocarbyl, an inert functional group, or taken together with R7 or R4 to form a ring, R10 is hydrogen, optionally substituted hydrocarbyl, an inert functional group, or taken together with R9 or R4 to form a ring, R11 is hydrogen, optionally substituted hydrocarbyl, an inert functional group, or taken together with R12 or R5 to form a ring, R15 is hydrogen, optionally substituted hydrocarbyl, an inert functional group, or taken together with R14 or R5 to form a ring, provided that R13 and at least one of R12 and R14 are independently selected from optionally substituted C1-C30 alkyl, optionally substituted C4-C30 alkyloxy, halogen and optionally substituted C5-C20 aryl, or R13 taken together with R12 or R14 form a ring, or R12 taken together with R11 form a ring and R14 taken together with R15 form a ring, and provided that at least one of R12, R13 and R14 is optionally substituted C4-C30 alkyloxy; M is a transition metal atom in particular selected from Ti, V, Cr, Mn, Fe, Co, Ni, Pd, Rh, Ru, Mo, Nb, Zr, Hf, Ta, W, Re, Os, Ir or Pt; n matches the formal oxidation state of the transition metal atom M; and X is halide, optionally substituted hydrocarbyl, alkoxide, amide, or hydride. The transition metal complexes of the present invention, their complexes with non-coordinating anions and catalyst systems containing such complexes have good solubility in non-polar media and chemically inert non-­polar solvents especially aromatic hydrocarbon solvents. The catalyst systems can be used for a wide range of (co­)oligomerization, polymerization and dimerization reactions.

  一种过渡金属配合物，为双芳胺吡啶MXn配合物，包括具有化学式(I)的双芳胺吡啶配体，其中R1-R5、R7-R9、R12和R14分别为独立的氢、可选择取代的烃基、惰性官能团，或R1-R3和R7-R9中的任意两个邻位取代基可以形成环，R6为氢、可选择取代的烃基、惰性官能团，或与R7或R4一起形成环，R10为氢、可选择取代的烃基、惰性官能团，或与R9或R4一起形成环，R11为氢、可选择取代的烃基、惰性官能团，或与R12或R5一起形成环，R15为氢、可选择取代的烃基、惰性官能团，或与R14或R5一起形成环，其中R13和至少一个R12和R14独立地选自可选择取代的C1-C30烷基、可选择取代的C4-C30烷氧基、卤素和可选择取代的C5-C20芳基，或R13与R12或R14一起形成环，或R12与R11一起形成环，R14与R15一起形成环，且至少一个R12、R13和R14为可选择取代的C4-C30烷氧基；M为过渡金属原子，特别选自Ti、V、Cr、Mn、Fe、Co、Ni、Pd、Rh、Ru、Mo、Nb、Zr、Hf、Ta、W、Re、Os、Ir或Pt；n与过渡金属原子M的形式氧化态相匹配；X为卤素、可选择取代的烃基、烷氧基、酰胺或氢化物。本发明的过渡金属配合物及其与非配位阴离子的复合物和含有此类配合物的催化系统在非极性介质和化学惰性非极性溶剂中具有良好的溶解性，特别是芳香烃类溶剂。该催化系统可用于广泛的(共)寡聚化、聚合和二聚化反应。
• A Novel [OSSO]‐Type Chromium(III) Complex as a Versatile Catalyst for Copolymerization of Carbon Dioxide with Epoxides
  作者：Francesco Della Monica、Veronica Paradiso、Alfonso Grassi、Stefano Milione、Luigi Cavallo、Carmine Capacchione

  DOI：10.1002/chem.201905455

  日期：2020.4.24

  A new chromium(III) complex, bearing a bis-thioether-diphenolate [OSSO]-type ligand, was found to be an efficient catalyst in the copolymerization of CO2 and epoxides to achieve poly(propylene carbonate), poly(cyclohexene carbonate), poly(hexene carbonate) and poly(styrene carbonate), as well as poly(propylene carbonate)(cyclohexene carbonate) and poly(propylene carbonate)(hexene carbonate) terpolymers

  发现一种带有双硫醚二酚[OSSO]型配体的新型铬（III）络合物是CO2和环氧化物共聚以获得聚碳酸丙烯酯，聚碳酸环己酯的有效催化剂，聚（碳酸己烯）和聚（碳酸苯乙烯），以及聚（碳酸亚丙酯）（碳酸环己烯）和聚（碳酸亚丙酯）（碳酸己烯）三元共聚物。
• Extremely Active Ethylene Tetramerization Catalyst Avoiding the Use of Methylaluminoxane: [iPrN{P(C ₆ H ₄ ‐ <i>p</i> ‐SiR ₃ ) ₂ } ₂ CrCl ₂ ] ⁺ [B(C ₆ F ₅ ) ₄ ] ⁻
  作者：Hee Soo Park、Tae Hee Kim、Jun Won Baek、Hyun Ju Lee、Tae Jin Kim、Ji Yeon Ryu、Junseong Lee、Bun Yeoul Lee

  DOI：10.1002/cctc.201900898

  日期：2019.9.5

  iPrN[P(C6H4‐p‐Si(nBu)3)2]2 (2) as well as from simply reacting 2 with [CrCl2(NCCH3)4]+[B(C6F5)4]−. The bulky (nBu)3Si‐substituents play the crucial role of preventing the formation of the inactive [(PNP)2CrCl2]+[B(C6F5)4]−. The prepared [2‐CrCl2]+[B(C6F5)4]− combined with iBu3Al was extremely active (>4000 kg/g‐Cr/h), performed well at a high temperature of up to 90 °C, and generated a negligible amount of PE

  Sasol最初的乙烯四聚催化剂需要使用昂贵的MMAO，较低的工作温度（约60°C），并会产生聚乙烯（PE）作为副产物。在这项研究中，我们开发了升级的催化系统，成功地避免了对MMAO的需求。[（PNP）CrCl 2 ] + [B（C 6 F 5）4 ] -型物质是通过CrCl 3（THF）3，[PhN（H）Me 2 ] + [B（C 6 F 5）4 ] - ，和iPrN [P（C 6 H ^ 4 - p-Si（nBu）3）2 ] 2（2）以及简单地将2与[CrCl 2（NCCH 3）4 ] + [B（C 6 F 5）4 ] -反应。庞大的（nBu）3 Si取代基在防止非活性[[PNP）2 CrCl 2 ] + [B（C 6 F 5）4 ] -的形成中起着至关重要的作用。制备的[ 2 -CrCl 2 ] +[B（C 6 F 5）4 ] -与iBu 3 Al结合时非常活泼（> 4000 kg /