sodium 4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxylate | 405082-09-9

• 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: sodium 4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxylate
• 英文别名: Sodium;2,6-bis(4-fluorophenyl)benzoate
• CAS: 405082-09-9
• 化学式: C₁₉H₁₁F₂O₂*Na
• 分子量: 332.282
• InChiKey: STVLHJXOBOQLOB-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  0.67
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  40.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,5-二甲基吡唑 、 nickel(II) nitrate hexahydrate 、 sodium 4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxylate 以 四氢呋喃 为溶剂， 以50%的产率得到bis(2,6-di-(p-fluorophenyl)benzoate)bis(3,5-dimethylpyrazole)nickel(II)
  参考文献：
  名称：

  Mononuclear transition metal complexes with sterically hindered carboxylate ligands: Synthesis, structural and spectral properties

  摘要：

  The metal coordination geometry in the active site of metalloproteins are very different from the one of small inorganic complexes, due to the inflexibility of the ligand set from amino acid side chains different from freely moving ligand set in synthesis. Using the sterically hindered 2,6-di-(p-fluorophenyl)benzoate(L) ligand, a series of mononuclear Co(II), Ni(II) and Cu(II) complexes of general formula [M(L)(2)(Hdmpz)(2)] (where, Hdmpz = 3,5-dimethyl pyrazole) have been synthesized and characterized by the variety of spectroscopic methods. A distorted octahedral geometry in case of nickel, tetrahedral geometry for cobalt and square pyramidal in copper was observed in the X-ray studies, which also revealed that the uncoordinated oxygen atom of the carboxylate group forms intramolecular hydrogen bonding with the N-H group of the coordinated 3,5-dimethylpyrazole in case of cobalt and copper. Crown Copyright (C) 2010 Published by Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2010.10.019
• 作为产物：
  描述：

  4,4''-difluoro-[1,1':3',1''-terphenyl]-2'-carboxylic acid 在 sodium hydroxide 作用下， 以 甲醇 为溶剂， 生成 sodium 4,4''-difluoro-1,1':3',1''-terphenyl-2'-carboxylate
  参考文献：
  名称：

  Water is a key factor to alter the structure and electrochemical properties of carboxylate-bridged dimanganese(ii) complexes

  摘要：

  三种锰配合物具有{Mn₂(μ-O₂CR)}³⁺，{Mn₂(μ-OH₂)₂(μ-O₂CR)}³⁺和{Mn₂(OH₆)₂(O₂CR)}³⁺结构，处于动态平衡状态，显示出明显不同的电化学性质，范围从0.52 V到1.19 Vvs.Fc/Fc⁺。

  DOI：

  10.1039/c4dt00520a

文献信息

• 큐베인 클러스터형의 촉매, 이의 합성방법 및 이를 이용한 올레핀의 에폭시화 방법
  申请人：Foundation for Research and Business, Seoul National University of Science and Technology 서울과학기술대학교 산학협력단(220040210013) BRN ▼210-82-08420

  公开号：KR20170128840A

  公开（公告）日：2017-11-24

  본 발명은 큐베인 클러스터형의 촉매, 이의 합성 방법 및 이를 이용한 올레핀의 에폭시화 방법에 관한 것으로, 더욱 상세하게는 탄화수소의 산화반응 촉매로 사용되는 코발트 금속 착물, 이의 합성 방법 및 이를 이용한 올레핀의 에폭시화 방법에 관한 것이다. 본 발명의 일 실시례에 따른 올레핀의 에폭시화 방법은, (a) Cubane cluster형의 코발트 착화합물을 합성하는 단계(S10)와, (b) 상기 Cubane cluster형의 코발트 착화합물을 촉매로 사용하여, 아세토니트릴(acetonitrile)(CHCN)과 메틸렌클로라이드(methylene chloride)(CHCl)의 부피비 1:1의 용매에 대하여 올레핀(olefin)을 기질로 사용하여, 산화제인 mCPBA(meta-Chloroperoxybenzoic acid)를 첨가하는 단계(S20)를 통해; (c) 상온에서 에폭시화반응을 진행시키는 단계를 포함하는 올레핀의 에폭시화 방법을 제공한다.

  本发明涉及立方簇状催化剂、其合成方法以及用于烯烃环氧化的方法，更详细地涉及用作烃氧化反应催化剂的钴金属络合物的立方簇状结构、其合成方法以及用于烯烃环氧化的方法。根据本发明的一种实施例，烯烃的环氧化方法包括以下步骤：(a)合成立方簇状钴络合物的步骤(S10)，(b)使用上述立方簇状钴络合物作为催化剂，在乙腈和氯化亚甲烷体积比为1:1的溶剂中以烯烃为底物，在添加过氧苯甲酸的条件下进行环氧化反应的步骤(S20)；(c)提供包括在室温下进行环氧化反应的步骤的烯烃的环氧化方法。
• Structural Characterization of [Zn(O₂CAr^4F^-Ph)₂(TAD)] and Determination of Its Stable Conformation by DFT Calculations
  作者：Namseok Kim、Il Hyun Baek、Sungho Yoon

  DOI：10.1002/bkcs.10775

  日期：2016.6

  axial carboxylate ligands, is located in a hexacoordinate ZnO2N4 environment. Two strong intra‐molecular hydrogen‐bonding interactions (CO⋯ H—N) between the carboxylate ligand and amine are observed, in addition to two weak intra‐molecular interactions among the aromatic C—H moieties and oxygen atoms of the carboxylate ligand. An inter‐molecular interaction is also detected between the aromatic C—H of

  在标题为[Zn（C 19 H 11 O 2 F 2）2（C 8 H 22 N 4）]∙0.5CH 2 Cl 2的配合物中，具有两个轴向羧酸盐配体的Zn 2+阳离子位于一个六配位ZnO 2 N 4环境。羧酸酯配体和胺之间观察到两个强的分子内氢键相互作用（CO⋯H-N），此外芳香族CH-H部分和羧酸酯配体的氧原子之间还存在两个弱的分子内相互作用。在羧酸盐配体的芳族CH与另一个羧酸盐配体的氟原子之间也检测到分子间相互作用。根据B3LYP / LANL2DZ计算，如在晶体结构中观察到的，当轴向羧酸盐的OCO部分的平面垂直时，可以达到标题配合物的最小能量。
• Synthetic Analogue of the {Fe₂(μ-OH)₂(μ-O₂CR)}³⁺ Core of Soluble Methane Monooxygenase Hydroxylase via Synthesis and Dioxygen Reactivity of Carboxylate-Bridged Diiron(II) Complexes
  作者：Dongwhan Lee、Stephen J. Lippard

  DOI：10.1021/ic011008s

  日期：2002.2.1

  and dioxygen reactivity of diiron(II) tetracarboxylate complexes [Fe(2)(mu-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(N,N-Me(2)en)(2)] (2) and [Fe(2)(mu-O(2)CAr(Tol))(2)(O(2)CAr(Tol))(2)(N,N-Bn(2)en)(2)] (6), where Ar(Tol)CO(2)(-) = 2,6-di(p-tolyl)benzoate. These complexes were prepared as models for the diiron(II) center in the hydroxylase component of soluble methane monooxygenase (MMOH). Compound 6 reacts

  我们描述了二羧酸二铁（II）配合物[Fe（2）（mu-O（2）CAr（Tol））（2）（O（2）CAr（Tol））（2）（N， N-Me（2）en）（2）]（2）和[Fe（2）（mu-O（2）CAr（Tol））（2）（O（2）CAr（Tol））（2）（ N，N-Bn（2）en）（2）]（6），其中Ar（Tol）CO（2）（-）= 2,6-二（对甲苯基）苯甲酸酯。这些络合物被制备为可溶甲烷单加氧酶（MMOH）羟化酶组分中二铁（II）中心的模型。在二胺配体上的侧基苄基氧化N-脱烷基后，化合物6与双氧反应以提供大约60（5）％的收率的PhCHO。二铁（III）配合物[Fe（2）（mu-OH）（2）（mu-O（2）CAr（Tol））（O（2）CAr（Tol））（3）（N-Bnen）（从反应混合物中分离出N，N-Bn（2）en）]（8）。4.2 KMössbauer光谱为8，显示了一个单四极子双峰，其参数delta
• Di- and tetra-bridged diiron(II) complexes with four terphenyl-derived carboxylates and two water molecules
  作者：Sungho Yoon、Amy E. Kelly、Stephen J. Lippard

  DOI：10.1016/j.poly.2004.06.019

  日期：2004.11

  Abstract New diiron(II) complexes having ligated water molecules were prepared and characterized by X-ray crystallography, IR spectroscopy and cyclic voltammetry. The compound [Fe2(OH2)2(μ-O2CAr4F-Ph)2(O2CAr4F-Ph)2(THF)2] (1), where −O2CAr4F-Ph is 2,6-di-(p-fluorophenyl)benzoate, has two distorted trigonal bipyramidal Fe(II) centers linked by two sterically hindered carboxylate ligands. The related molecules

  摘要制备了具有连接水分子的新型二铁（II）配合物，并通过X射线晶体学，红外光谱和循环伏安法对其进行了表征。化合物[Fe2（OH2）2（μ-O2CAr4F-Ph）2（O2CAr4F-Ph）2（THF）2]（1），其中-O2CAr4F-Ph为2,6-二-（对氟苯基）苯甲酸酯，具有两个扭曲的三角双锥体Fe（II）中心，由两个空间位阻的羧酸盐配体连接。相关分子[Fe2（μ-OH2）2（μ-O2CArTol）2（O2CArTol）2（THF）2]（2）和[Fe2（μ-OH2）2（μ-O2CArTol）2（O2CArTol）2（ 4-tBuC5H4N）2]（3），其中-O2CArTol为2,6-二-（对甲苯基）苯甲酸酯，4-tBuC5H4N为4-叔丁基吡啶，含有四桥联二铁（II）核，中心Fe2（OH2）2平面四边形。振动光谱和电化学测量表明，3的连接水分子在结合和自由形式之间处于平衡状态。
• Modeling Dioxygen-Activating Centers in Non-Heme Diiron Enzymes:  Carboxylate Shifts in Diiron(II) Complexes Supported by Sterically Hindered Carboxylate Ligands
  作者：Dongwhan Lee、Stephen J. Lippard

  DOI：10.1021/ic020186y

  日期：2002.5.1

  General synthetic routes are described for a series of diiron(II) complexes supported by sterically demanding carboxylate ligands 2,6-di(p-tolyl)benzoate ((ArCO2-)-C-Tol) and 2,6-di(4-fluorophenyl)benzoate (Ar4-FPhCO2-). The interlocking nature of the m-terphenyl units in self-assembled [Fe-2(mu-O2CArTol)(2)(O2CArTol)(2)L-2] (L = C5H5N (4); 1-Melm (5)) promotes the formation of coordination geometries analogous to those of the non-heme diiron cores in the enzymes RNR-R2 and Delta9D. Magnetic susceptibility and Mossbauer studies of 4 and 5 revealed properties consistent with weak antiferromagnetic coupling between the high-spin iron(II) centers. Structural studies of several derivatives obtained by ligand substitution reactions demonstrated that the [Fe-2(O2CAr')(4)L-2] (Ar' = Ar-Tol; Ar4-FPh) module is geometrically flexible. Details of ligand migration within the tetracarboxylate diiron core, facilitated by carboxylate shifts, were probed by solution variable-temperature F-19 NMR spectroscopic studies of [Fe-2(mu-O2CAr4-FPh)(2)(O2CAr4-FPh)(2)(THF)(2)] (8) and [Fe-2(mu-O2CAr4-FPh)(4)(4-(BuC5H4N)-Bu-1)(2)] (12). Dynamic motion in the primary coordination sphere controls the positioning of open sites and regulates the access of exogenous ligands, processes that also occur in non-heme diiron enzymes during catalysis.