1,8-bis(2,2':6',2"-terpyrid-4'-yl)anthracene | 272113-72-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 1,8-bis(2,2':6',2"-terpyrid-4'-yl)anthracene
• 英文别名: 1,8-bis(2,2′:6′,2″-terpyrid-4′-yl)anthracene；btpyan；1,8-bis(2,2':6',2''-terpyridyl)anthracene；1,8-bis(2,2':6',2''-terpyrid-4'-yl)anthracene；4-[8-(2,6-Dipyridin-2-ylpyridin-4-yl)anthracen-1-yl]-2,6-dipyridin-2-ylpyridine
• CAS: 272113-72-1
• 化学式: C₄₄H₂₈N₆
• 分子量: 640.747
• InChiKey: VKRVUSPJWOLYEW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  50
• 可旋转键数：
  6
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  77.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,8-bis(2,2':6',2"-terpyrid-4'-yl)anthracene 、 三氯化钌 以 甲醇 为溶剂， 以68%的产率得到[Ru2Cl6(1,8-bis(2,2':6',2''-terpyridyl)anthracene)]*5H2O
  参考文献：
  名称：

  Syntheses and Redox Properties of Bis(hydroxoruthenium) Complexes with Quinone and Bipyridine Ligands. Water-Oxidation Catalysis

  摘要：

  The novel bridging ligand 1,8-bis(2,2':6',2"-terpyridyl)anthracene (btpyan) is synthesized by three reactions from 1,8-diformylanthracene to connect two [Ru(L)(OH)](+) units (L = 3,6-di-tert-butyl-1,2;benzoquinone (3,6-Bu-t(2)-qui) and 2,2'-bipyridine (bpy)). An addition of (BuOK)-Bu-t (2.0 equiv) to a methanolic solution of [Ru-2(II)(OH)(2)(3,6-(t)Bu(2)qui)(2)(btpyan)](SbF6)(2) ([1](SbF6)(2)) results in the generation of [Ru-2(II)(O)(2)(3,6-(t)Bu(2)sq)(2)(btpyan)](0) (3,6-(t)Bu(2)sq = 3,6 -di-tert-butyl-1,2-semiquinone) due to the reduction of quinone coupled with the dissociation of the hydroxo protons. The resultant complex [Ru-2(II)(O)(2)(3,6-(t)Bu(2)sq)(2)(btpyan)](0) undergoes ligand-localized oxidation at E-1/2 = +0.40 V (vs Ag/AgCl) to give [Ru-2(II)(O)(2)(3,6-(t)Bu(2)qui)(2)(btpyan)](2+) in MeOH solution: Furthermore, metal-localized oxidation of [Ru-2(II)(O)(2)(3, 6-(t)Bu(2)qui)(2)(btpyan)](2+) at E-p = + 1.2 V in CF3CH2OH/etheq or water gives [Ru-2(III)(O)(2)(3,6-(t)Bu(2)qui)(2)(btpyan)](4+), which catalyzes water oxidation. Controlled-potential electrolysis of [1](SbF6)(2) at +1.70 V in the presence of H2O in CF3CH2OH evolves dioxygen with a current efficiency of 91% (21 turnovers). The turnover number of O-2 evolution increases to 33 500 when the electrolysis is conducted in water (pH 4.0) by using a [1](SbF6)(2)-modified ITO electrode. On the other hand, the analogous complex [Ru-2(II)(OH)(2)(bpy)(2)(btpyan)](SbF6)(2) ([2](SbF6)(2)) shows neither dissociation of the hydroxo protons, even in the presence of a large excess of (BuOK)-Bu-t, nor activity for the oxidation of H2O under similar conditions.

  DOI：

  10.1021/ic000552i
• 作为产物：
  描述：

  1,8-二氯蒽 在 tris-(dibenzylideneacetone)dipalladium(0) 、 四(三苯基膦)钯 、 sodium acetate 、 sodium carbonate 、 二乙醇胺 、 2-二环己基磷-2,4,6-三异丙基联苯 作用下， 以 1,4-二氧六环 、 乙醚 、 N,N-二甲基甲酰胺 、 异丙醇 为溶剂， 反应 51.0h， 生成 1,8-bis(2,2':6',2"-terpyrid-4'-yl)anthracene
  参考文献：
  名称：

  双（钌-二氧杂环丁烯-三吡啶）配合物对水氧化的取代基依赖性能力†

  摘要：

  桥联配体1,8-双（2,2'：6'，2''-terpyrid-4'-基）蒽（btpyan）是通过蒽浦-1,8-蒽的Miyaura-Suzuki交叉偶联反应合成的在Pd（PPh 3）4（5 mol％）存在下，用二硼酸和4'-triflyl-2,2'：6'-2''-叔吡啶实现收率68％。三钌二氧戊环二聚物，的[Ru 2（OH）2（二氧杂环戊烯）2（btpyan）] 0（二氧戊环＝ 3，6-二叔丁基-1,2-苯并半醌（[ 1 ] 0），3,5-二氯-1,2-苯并半醌（[ 2 ] 0）和4-硝基-1,2-苯并半醌（[ 3 ] 0））是通过[Ru 2 Cl 6（btpyan）] 0与相应的邻苯二酚反应制备的。[ 1 ] 0的电子结构近似为[Ru II 2（OH）2（sq）2（btpyan）] 0（sq =半喹诺酮）。另一方面，[ 2 ] 0的电子状态和[ 3 ] 0接近[Ru III 2（OH）2（cat）2（btpyan）]

  DOI：

  10.1039/c0dt00977f

文献信息

• Tuning Oxygen Reduction Catalysis of Dinuclear Cobalt Polypyridyl Complexes by the Bridging Structure
  作者：Hiroaki Arima、Misato Wada、Takashi Nakazono、Tohru Wada

  DOI：10.1021/acs.inorgchem.1c00293

  日期：2021.7.5

  The four-electron oxygen reduction reaction (4e–-ORR) is the mainstay in chemical energy conversion. Elucidation of factors influencing the catalyst’s reaction rate and selectivity is important in the development of more active catalysts of 4e–-ORR. In this study, we investigated chemical and electrochemical 4e–-ORR catalyzed by Co2(μ-O2) complexes bridged by xanthene (1) and anthracene (3) and by

  四电子氧还原反应 (4e – -ORR) 是化学能转化的中流砥柱。阐明影响催化剂反应速率和选择性的因素对于开发更具活性的4e -- ORR催化剂具有重要意义。在这项研究中，我们调查的化学和电化学4E - -ORR的Co催化2（μ-O 2）络合物桥接由呫吨（1）和蒽（3）和通过共2（OH）2配合物的蒽醌桥接（2）。在使用 Fe(CpMe) 2作为酸性 PhCN 还原剂的化学 ORR中，我们发现1在三个复合物中显示出最高的初始周转频率（TOF init = 6.8 × 10 2 s –1）和对 4e – -ORR 的选择性（96%）。的详细动力学分析已经揭示，所述速率确定步骤（RDS中）中的催化循环1 - 3具有将O 2添加到[CO II 2（OH 2）2 ] 4+作为共同中间体。在络合物1用作催化剂的唯一情况下，k cat取决于质子浓度，因为 O 2添加到 [CoII 2 (OH 2 ) 2
• Four-electron reduction of dioxygen catalysed by dinuclear cobalt complexes bridged by bis(terpyridyl)anthracene
  作者：Tohru Wada、Hidetaka Maki、Tomoyuki Imamoto、Hirokazu Yuki、Yuji Miyazato

  DOI：10.1039/c2cc36528f

  日期：——

  Dinuclear cobalt-1,10-phenanthroline (1) and 2,2′-bipyridine (2) complexes bridged by 1,8-bis(2,2′:6′,2′′-terpyrid-4′-yl)anthracene (btpyan) were prepared. Both of the complexes selectively catalysed the electrochemical four-electron reduction of dioxygen to H2O without the generation of H2O2 as a two-electron reduction product.

  制备了由 1,8-双(2,2′:6′,2′′-三吡啶-4′-基)蒽（btpyan）桥接的双核钴-1,10-菲罗啉（1）和 2,2′-联吡啶（2）配合物。这两种络合物都能选择性地催化二氧到 H2O 的电化学四电子还原反应，而不会生成作为双电子还原产物的 H2O2。
• JP6146860
  申请人：——

  公开号：——

  公开（公告）日：——
• Substituents dependent capability of bis(ruthenium-dioxolene-terpyridine) complexes toward water oxidation
  作者：Tohru Wada、James T. Muckerman、Etsuko Fujita、Koji Tanaka

  DOI：10.1039/c0dt00977f

  日期：——

  The bridging ligand, 1,8-bis(2,2′:6′,2′′-terpyrid-4′-yl)anthracene (btpyan) was synthesized by the Miyaura-Suzuki cross coupling reaction of anthracenyl-1,8-diboronic acid and 4′-triflyl-2,2′:6′-2′′-terpyridine in the presence of Pd(PPh3)4 (5 mol%) with 68% in yield. Three ruthenium-dioxolene dimers, [Ru2(OH)2(dioxolene)2(btpyan)]0 (dioxolene = 3,6-di-tert-butyl-1,2-benzosemiquinone ([1]0), 3,5-dichloro-1

  桥联配体1,8-双（2,2'：6'，2''-terpyrid-4'-基）蒽（btpyan）是通过蒽浦-1,8-蒽的Miyaura-Suzuki交叉偶联反应合成的在Pd（PPh 3）4（5 mol％）存在下，用二硼酸和4'-triflyl-2,2'：6'-2''-叔吡啶实现收率68％。三钌二氧戊环二聚物，的[Ru 2（OH）2（二氧杂环戊烯）2（btpyan）] 0（二氧戊环＝ 3，6-二叔丁基-1,2-苯并半醌（[ 1 ] 0），3,5-二氯-1,2-苯并半醌（[ 2 ] 0）和4-硝基-1,2-苯并半醌（[ 3 ] 0））是通过[Ru 2 Cl 6（btpyan）] 0与相应的邻苯二酚反应制备的。[ 1 ] 0的电子结构近似为[Ru II 2（OH）2（sq）2（btpyan）] 0（sq =半喹诺酮）。另一方面，[ 2 ] 0的电子状态和[ 3 ] 0接近[Ru III 2（OH）2（cat）2（btpyan）]
• Syntheses and Redox Properties of Bis(hydroxoruthenium) Complexes with Quinone and Bipyridine Ligands. Water-Oxidation Catalysis
  作者：Tohru Wada、Kiyoshi Tsuge、Koji Tanaka

  DOI：10.1021/ic000552i

  日期：2001.1.1

  The novel bridging ligand 1,8-bis(2,2':6',2"-terpyridyl)anthracene (btpyan) is synthesized by three reactions from 1,8-diformylanthracene to connect two [Ru(L)(OH)](+) units (L = 3,6-di-tert-butyl-1,2;benzoquinone (3,6-Bu-t(2)-qui) and 2,2'-bipyridine (bpy)). An addition of (BuOK)-Bu-t (2.0 equiv) to a methanolic solution of [Ru-2(II)(OH)(2)(3,6-(t)Bu(2)qui)(2)(btpyan)](SbF6)(2) ([1](SbF6)(2)) results in the generation of [Ru-2(II)(O)(2)(3,6-(t)Bu(2)sq)(2)(btpyan)](0) (3,6-(t)Bu(2)sq = 3,6 -di-tert-butyl-1,2-semiquinone) due to the reduction of quinone coupled with the dissociation of the hydroxo protons. The resultant complex [Ru-2(II)(O)(2)(3,6-(t)Bu(2)sq)(2)(btpyan)](0) undergoes ligand-localized oxidation at E-1/2 = +0.40 V (vs Ag/AgCl) to give [Ru-2(II)(O)(2)(3,6-(t)Bu(2)qui)(2)(btpyan)](2+) in MeOH solution: Furthermore, metal-localized oxidation of [Ru-2(II)(O)(2)(3, 6-(t)Bu(2)qui)(2)(btpyan)](2+) at E-p = + 1.2 V in CF3CH2OH/etheq or water gives [Ru-2(III)(O)(2)(3,6-(t)Bu(2)qui)(2)(btpyan)](4+), which catalyzes water oxidation. Controlled-potential electrolysis of [1](SbF6)(2) at +1.70 V in the presence of H2O in CF3CH2OH evolves dioxygen with a current efficiency of 91% (21 turnovers). The turnover number of O-2 evolution increases to 33 500 when the electrolysis is conducted in water (pH 4.0) by using a [1](SbF6)(2)-modified ITO electrode. On the other hand, the analogous complex [Ru-2(II)(OH)(2)(bpy)(2)(btpyan)](SbF6)(2) ([2](SbF6)(2)) shows neither dissociation of the hydroxo protons, even in the presence of a large excess of (BuOK)-Bu-t, nor activity for the oxidation of H2O under similar conditions.