2-(2'-hydroxy-5'-bromophenyl)-1,3-bis[3'-aza-4'-(2''-hydroxy-5''-bromophenyl)-but-4'-en-1'-yl]-1,3-imidazolidine | 161808-43-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: 2-(2'-hydroxy-5'-bromophenyl)-1,3-bis[3'-aza-4'-(2''-hydroxy-5''-bromophenyl)-but-4'-en-1'-yl]-1,3-imidazolidine
• 英文别名: 2-(5-bromo-2-hydroxyphenyl)-1,3-bis[4-(5-bromo-2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine；2-(5-bromo-2-hydroxyphenyl)-1,3-bis[4-(5-bromo-2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazoline；2-(5-bromo-2-hydroxyphenyl)-1,3-bis[4-(5-bromo-2-hydroxyphenyl)-3-azabut-3-enyl]imidazolidine；2-(5-bromo-2-hydroxyphenyl)-1,3-bis(2-(5-bromo-2-hydroxybenzylideneamino)ethyl)imidazolidine；4-Bromo-2-[2-[2-(5-bromo-2-hydroxyphenyl)-3-[2-[(5-bromo-2-hydroxyphenyl)methylideneamino]ethyl]imidazolidin-1-yl]ethyliminomethyl]phenol
• CAS: 161808-43-1
• 化学式: C₂₇H₂₇Br₃N₄O₃
• 分子量: 695.248
• InChiKey: MPSBMKVQDPLADP-UHFFFAOYSA-N

物化性质

• 熔点：
  156-158 °C
• 沸点：
  700.8±60.0 °C(Predicted)
• 密度：
  1.68±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  37
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  91.9
• 氢给体数：
  3
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  lanthanum(III) nitrate hexahydrate 、 2-(2'-hydroxy-5'-bromophenyl)-1,3-bis[3'-aza-4'-(2''-hydroxy-5''-bromophenyl)-but-4'-en-1'-yl]-1,3-imidazolidine 在 sodium acetate 作用下， 以 甲醇 、 氯仿 为溶剂， 生成
  参考文献：
  名称：

  Yang, Li-Wei; Liu, Shuang; Wong, Ernest, Inorganic Chemistry, 1995, vol. 34, # 8, p. 2164 - 2178

  摘要：

  DOI：
• 作为产物：
  描述：

  三乙烯四胺 、 5-溴水杨醛 以 甲醇 为溶剂， 生成 2-(2'-hydroxy-5'-bromophenyl)-1,3-bis[3'-aza-4'-(2''-hydroxy-5''-bromophenyl)-but-4'-en-1'-yl]-1,3-imidazolidine
  参考文献：
  名称：

  双核钴（III）配位化合物在分子氧还原反应中的电催化性能

  摘要：

  一种新的双核钴（III）配位化合物，[CO 2 L（μ-N 3）（N 3）2 ]·CH 3 OH（1），合成和表征通过元素分析，光谱方法，和单晶X射线分析，其中H 3 L是七亚乙基配体，是通过三亚乙基四胺与5-溴-2-羟基苯甲醛缩合获得的。X射线分析表明，两个钴（III）离子扭曲了八面体的几何形状，并通过苯氧基和叠氮桥联配体连接在一起。研究了化合物1对氧（O 2）还原反应的催化活性。化合物1可以在极化水–1,2-二氯乙烷界面有效地催化弱电子给体二茂铁（Fc）还原O 2。发现化合物1可以催化O 2还原为H 2 O 2，而在Fc存在下，其可以催化O 2还原为水。

  DOI：

  10.1002/aoc.5214

文献信息

• Design of chiral homodinuclear complexes based on the coordinating behaviour of some symmetric ligands
  作者：Ana M. García-Deibe、Matilde Fondo、Noelia Ocampo、Jesús Sanmartín、Esther Gómez-Fórneas

  DOI：10.1039/c0nj00071j

  日期：——

  The crystal structures determined for [Zn2L1(acac)]·H2O and [Zn2L2(acac)]·H2O·MeCN·MeOH show that both compounds are chiral, although crystallising as racemates. This was not unexpected, as these complexes had been designed on the basis of the coordinating behaviour of acac in combination with 2-(2-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine (H3L1) and 2-(5-bromo-2-hydroxyphenyl)-1,3-bis[4-(5-bromo-2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine (H3L2). The reactivity of Zn(acac)2·nH2O with compartmental H3Lx (x = 1 or 2) has been investigated under different reaction conditions. Thus, depending on the temperature, the reaction with H3L1 can yield [Zn2L1(acac)]·H2O or [Zn2L1(OAc)]·H2O, whilst the interaction of Zn(acac)2·nH2O with H3L2 only gives rise to crystalline [Zn2L2(acac)]·H2O·MeCN·MeOH. This latter species loses the most volatile solvates on drying to yield [Zn2L2(acac)]·H2O. Both [Zn2Lx(acac)]·H2O complexes have been fully characterised by analytical and spectroscopic methods.

  为[Zn2L1(acac)]-H2O 和[Zn2L2(acac)]- -MeCN-MeOH 确定的晶体结构显示，这两种化合物都是手性的，尽管结晶为外消旋体。这并不出乎意料，因为这些配合物是根据 acac 与 2-(2-羟基苯基)-1,3-双[4-(2-羟基苯基)-3-氮杂丁-3-烯基]-1,3-咪唑烷 (H3L1) 和 2-(5-溴-2-羟基苯基)-1,3-双[4-(5-溴-2-羟基苯基)-3-氮杂丁-3-烯基]-1,3-咪唑烷 (H3L2) 的配位行为设计的。在不同的反应条件下，研究了 Zn（acac）2-n 与隔室 H3Lx（x = 1 或 2）的反应性。因此，根据温度的不同，与 H3L1 的反应可以产生 [Zn2L1(acac)]- 或 [Zn2L1(OAc)]- ，而 Zn(acac)2-n 与 H3L2 的相互作用只产生结晶的 [Zn2L2(acac)]- -MeCN-MeOH。后一种物质在干燥时会失去最易挥发的溶胶，生成[Zn2L2（acac）]- 。这两种[Zn2Lx(acac)]- 复合物都已通过分析和光谱方法进行了全面表征。
• One pot-synthesis of chiral Ni6 clusters involving Ni3 subunits: a combined structural, magnetic and DFT study
  作者：Matilde Fondo、Noelia Ocampo、Ana M. García-Deibe、Joan Cano、Jesús Sanmartín

  DOI：10.1039/c0dt00659a

  日期：——

  Ni6 clusters of the general formula [Ni3Ln(OAc)(OH)}2(X)(OAc)(H2O)2] (n = 1, 2; X = Cl− or N3−, (Ln)3− = hexadentate tritopic ligands) can be isolated by spontaneous self-assembly, from mixtures of Ni(OAc)2, H3Ln, NMe4OH·5H2O and NaX in adequate molar ratios. Thus, four new hexanuclear complexes [Ni3L1(OAc)(OH)}2Cl(OAc)(H2O)2]·7.5H2O (1·7.5H2O), [Ni3L2(OAc)(OH)}2Cl(OAc)(H2O)2]·2H2O·7.5MeOH (2·2H2O·7.5MeOH), [Ni3L1(OAc)(OH)}2(N3)(OAc)(H2O)2]·6H2O (3·6H2O) and [Ni3L2(OAc)(OH)}2(N3)(OAc)(H2O)2]·4H2O (4·4H2O) were obtained and fully characterised. 1·7.5H2O and 2·2H2O·7.5MeOH were isolated in the form of single crystals, the latter losing solvate on drying, to yield 2·2H2O. Recrystallisation of 3·6H2O in MeCN/MeOH also generates single crystals of 3·H2O·2MeOH·2MeCN. Their X-ray characterisation shows that these Ni6 clusters can be considered to be built from two triangular trinuclear [Ni3Ln(OAc)(OH)]+ subunits with different connectors. In addition, these studies demonstrate that the (Ln)3− ligands behave as trinucleating, adopting such a conformation that induces chirality in the isolated compounds. In this way, 3·H2O·2MeOH·2MeCN appears particularly interesting, since it emerges as homochiral after undergoing spontaneous resolution upon crystallisation. The magnetic characterisation of 1·7.5H2O to 3·6H2O reveals that the three compounds present an overall antiferromagnetic coupling. The intricate magnetic behaviour of these clusters, mediated by a total of 14 bridges of different kinds, was analysed and satisfactorily interpreted in light of DFT calculations.

  通式为[Ni3Ln(OAc)(OH)}2(X)(OAc)(H2O)2]的 Ni6 簇合物（n = 1、2；X = Cl- 或 N3-，(Ln)3- = 六价三位配体）可通过自发自组装从 Ni(OAc)2、H3Ln、NMe4OH-5 和 NaX 以适当摩尔比组成的混合物中分离出来。因此，四种新的六核配合物[Ni3L1（OAc）（OH）}2Cl（OAc）（ ）2]-7.5 （1-7.5 ）、[Ni3L2（OAc）（OH）}2Cl（OAc）（ ）2]-2 -7.5MeOH（2-2 -7.5MeOH）、[Ni3L1(OAc)(OH)}2(N3)(OAc)( )2]-6 （3-6 ）和[Ni3L2(OAc)(OH)}2(N3)(OAc)( )2]-4 （4-4 ）。以单晶形式分离出 1-7.5 和 2-2 -7.5MeOH，后者在干燥时失去溶解度，得到 2-2 。3-6 在 MeCN/MeOH 中重结晶也会生成 3- -2MeOH-2MeCN 的单晶。它们的 X 射线特征显示，这些 Ni6 团簇可视为由两个具有不同连接点的三角形三核 [Ni3Ln(OAc)(OH)]+ 亚基构建而成。此外，这些研究还表明，(Ln)3- 配体具有三核行为，其采用的构象诱导了分离化合物的手性。在这种情况下，3- -2MeOH-2MeCN 显得特别有趣，因为它在结晶时经历了自发解析后出现了同手性。对 1-7.5 和 3-6 进行的磁性分析表明，这三种化合物呈现出整体反铁磁耦合。根据 DFT 计算，分析并圆满解释了这些簇合物由总共 14 个不同类型的桥所介导的错综复杂的磁性行为。
• Dinuclear nickel complexes with a Ni₂O₂core: a structural and magnetic study
  作者：Matilde Fondo、Ana M. García-Deibe、Noelia Ocampo、Jesús Sanmartín、Manuel R. Bermejo、Antonio L. Llamas-Saiz

  DOI：10.1039/b606414k

  日期：——

  The acetylacetonate complexes [Ni2L1(acac)(MeOH)]·H2O, 1·H2O and [Ni2L3(acac)(MeOH)]·1.5H2O, 2·1.5H2O (H3L1 = (2-(2-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine and H3L3 = (2-(5-bromo-2-hydroxyphenyl)-1,3-bis[4-(5-bromo-2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine) were prepared and fully characterised. Their crystal structures show that they are dinuclear complexes, extended into chains by hydrogen bond interactions. These compounds were used as starting materials for the isolation of the corresponding [Ni2HLx(o-O2CC6H4CO2)(H2O)]·nMeOH and [Ni2HLx(O2CCH2CO2)(H2O)]·nH2O dicarboxylate complexes (x = 1, 3; n = 1–3). The crystal structures of [Ni2HL1(o-O2CC6H4CO2)(H2O)]·MeOH, 3·MeOH, [Ni2HL3(o-O2CC6H4CO2)(H2O)]·3MeOH, 4·3MeOH and [Ni2HL1(O2CCH2CO2)(H2O)]·2.5H2O·0.25MeOH·MeCN, 5·2.5H2O·0.25MeOH·MeCN, were solved. Complexes 3–5 show dinuclear [Ni2HLx(dicarboxylate)(H2O)] units, expanded through hydrogen bonds that involve carboxylate and water ligands, as well as solvate molecules. The variable temperature magnetic susceptibilities of all the complexes show an intramolecular ferromagnetic coupling between the Ni(II) ions, which is attempted to be rationalized by comparison with previous results and in the light of molecular orbital treatment. Magnetisation measurements are in accord with a S = 2 ground state in all cases.

  乙酰丙酮络合物[Ni2L1(acac)(MeOH)]-H2O，1- 和[Ni2L3(acac)(MeOH)]-1.5 ，2-1.5 （H3L1 = (2-(2-羟基苯基)-1,3-双[4-(2-羟基苯基)-3-氮杂丁-3-烯基]-1,3-咪唑烷)和 H3L3 = (2-(5-溴-2-羟基苯基)-1,3-双[4-(5-溴-2-羟基苯基)-3-氮杂丁-3-烯基]-1,3-咪唑烷)）。它们的晶体结构显示，它们是通过氢键相互作用延伸成链的双核复合物。这些化合物被用作起始材料，用于分离相应的 [Ni2HLx(o-O2CC6H4CO2)( )]-nMeOH 和 [Ni2HLx(O2CCH2CO2)( )]-n 二羧酸盐配合物（x = 1, 3; n = 1-3）。解决了 [Ni2HL1(o-O2CC6H4CO2)( )]-MeOH, 3-MeOH, [Ni2HL3(o-O2CC6H4CO2)( )]-3MeOH, 4-3MeOH 和 [Ni2HL1(O2CCH2CO2)( )]-2.5 -0.25MeOH-MeCN, 5-2.5 -0.25MeOH-MeCN 的晶体结构。配合物 3-5 显示出双核 [Ni2HLx(二羧酸盐)( )]单元，通过氢键扩展，涉及羧酸盐和水配体以及溶质分子。所有配合物的变温磁感应强度都显示出 Ni(II)离子之间存在分子内铁磁耦合。磁化测量结果与所有情况下的 S = 2 基态一致。
• Insights into the absorption of carbon dioxide by zinc substrates: isolation and reactivity of di- and tetranuclear zinc complexes
  作者：Matilde Fondo、Ana M. García-Deibe、Noelia Ocampo、Jesús Sanmartín、Manuel R. Bermejo

  DOI：10.1039/b405744a

  日期：——

  The heptadentate Schiff base H3L can react with zinc acetate to form the discrete dinuclear complex Zn2L(OAc)(H2O), 1·H2O. The reaction of 1·H2O with NMe4OH·5H2O both in air and under an argon stream has been investigated. On one hand, this reaction in air yields the tetranuclear complex (Zn2L)2(CO3)(H2O)6, 2·5H2O, by spontaneous absorption of adventitious carbon dioxide. This process can be reverted in an acetic acid medium, whereas the treatment of 2·5H2O with methanoic acid yields crystals of [Zn2L(HCOO)]·0.5MeCN·1.25MeOH·2H2O, 3·0.5MeCN·1.25MeOH·2H2O. On the other hand, the interaction under an argon atmosphere of 1·H2O with NMe4OH·5H2O in methanol allows the isolation of the dinuclear complex Zn2L(OMe)(H2O)4, 4·4H2O. Recrystallisations of 1·H2O, 2·5H2O and 4·4H2O, in different solvents, yielded single crystals of 1·MeCN·2.5H2O, 2·4MeOH and 4·3MeOH·H2O, respectively. The crystal structure of 2·4MeOH can be understood as resulting from an unusual asymmetric tetranuclear self-assembly from two dinuclear units, and shows three different geometries around the four zinc atoms.

  七齿希夫碱H3L可以与乙酸锌反应形成离散双核配合物Zn2L(OAc)(H2O), 1· 。研究了 1· 与 NMe4OH·5 在空气中和氩气流下的反应。一方面，该反应在空气中通过自发吸收外来二氧化碳产生四核配合物(Zn2L)2(CO3)( )6, 2·5 。该过程可以在乙酸介质中恢复，而用甲酸处理2·5 则得到[Zn2L(HCOO)]·0.5MeCN·1.25MeOH·2 、3·0.5MeCN·1.25MeOH·2 晶体。另一方面，在氩气氛下1· 与甲醇中的NMe4OH·5 相互作用可以分离出双核配合物Zn2L(OMe)( )4, 4·4 。 1· 、2·5 和4·4 在不同溶剂中重结晶，分别得到1·MeCN·2.5 、2·4MeOH和4·3MeOH· 的单晶。 2·4MeOH 的晶体结构可以理解为由两个双核单元不寻常的不对称四核自组装产生的，并在四个锌原子周围显示出三种不同的几何形状。
• Ferromagnetism in dinuclear copper(ii)-phenolate complexes with exogenous O-donor bridges: a comparative study
  作者：Matilde Fondo、Noelia Ocampo、Ana M. García-Deibe、Montserrat Corbella、Manuel R. Bermejo、Jesús Sanmartín

  DOI：10.1039/b507068f

  日期：——

  The copper(II) complex Cu2L(OAc)(H2O)3.5, 1·3.5H2O was obtained and its reactivity in a basic medium investigated. Complex 1·3.5H2O shows different reaction patterns in air and in an inert atmosphere. Accordingly, interaction of 1·3.5H2O with Me4NOH·5H2O in methanol–acetonitrile in air yields the hydroxide complex Cu2L(OH)(H2O)1.125, 2·1.125H2O while Cu2L(OMe)(MeOH)0.5(H2O), 3·0.5MeOH·H2O is isolated under an argon atmosphere. The products 1–3 were fully characterised and single crystals of [Cu2L(OAc)]·MeCN·3.5H2O}2, 1·MeCN·3.5H2O, [Cu2L(OH)]·MeCN·1.125H2O}2, 2·MeCN·1.125H2O and [Cu2L(OMe)]·0.5MeOH·H2O, 3·0.5MeOH·H2O solved. The single X-ray study shows that 1–3 are dinuclear complexes with an endogenous phenol oxygen and an exogenous O-bridge. Magnetic characterisation of the three dinuclear complexes was performed, showing an apparent anomalous intramolecular ferromagnetic coupling between the metal atoms in all cases.

  获得了铜(II)络合物Cu2L(OAc)(H2O)3.5, 1·3.5 并研究了其在碱性介质中的反应性。配合物1·3.5 在空气和惰性气氛中表现出不同的反应模式。因此，在空气中的甲醇-乙腈中，1·3.5 与 Me4NOH·5 相互作用，生成氢氧化物络合物 Cu2L(OH)( )1.125, 2·1.125 ，而 Cu2L(OMe)(MeOH)0.5( ), 3·在氩气氛下分离出0.5MeOH· 。产物1-3得到充分表征，单晶为[Cu2L(OAc)]·MeCN·3.5 }2, 1·MeCN·3.5 , [Cu2L(OH)]·MeCN·1.125 }2, 2 ·MeCN·1.125 和[Cu2L(OMe)]·0.5MeOH· 、3·0.5MeOH· 溶解。单次 X 射线研究表明，1-3 是具有内源酚氧和外源 O 桥的双核配合物。对三个双核配合物进行了磁性表征，显示在所有情况下金属原子之间都存在明显的异常分子内铁磁耦合。