4-(5-bromothiophen-2-yl)-6-phenyl-2,2'-bipyridine | 1301629-53-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 4-(5-bromothiophen-2-yl)-6-phenyl-2,2'-bipyridine
• CAS: 1301629-53-7
• 化学式: C₂₀H₁₃BrN₂S
• 分子量: 393.307
• InChiKey: VBFRIBKXKRCESG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.3
• 重原子数：
  24.0
• 可旋转键数：
  3.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  25.78
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-methoxy-N-(4-methoxyphenyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)aniline 、 4-(5-bromothiophen-2-yl)-6-phenyl-2,2'-bipyridine 在 四(三苯基膦)钯 、 potassium carbonate 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 14.0h， 生成 4-methoxy-N-(4-methoxyphenyl)-N-(4-(5-(6-phenyl-2,2'-bipyridin-4-yl)thiophen-2-yl)phenyl)aniline
  参考文献：
  名称：

  Systematic Modulation of a Bichromic Cyclometalated Ruthenium(II) Scaffold Bearing a Redox-Active Triphenylamine Constituent

  摘要：

  The syntheses and physicochemical properties of nine bis-tridentate ruthenium(II) complexes containing one cyclometalating ligand furnished with terminal triphenylamine (TPA) substituents are reported. The structure of each complex conforms to a molecular scaffold formulated as [Ru-II(TPA-2,5-thiophene-pbpy)(Me(3)tctpy)] (pbpy = 6-phenyl-2,2'-bipyridine; Me(3)tctpy = trimethyl-4,4',4 ''-tricarboxylate-2,2':6',2 ''-terpyridine), where various electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) are installed about the TPA unit and the anionic ring of the pbpy ligand. It is found that the redox chemistry of the Ru center and the TPA unit can be independently modulated by (i) placing EWGs (e.g., -CF3) or EDGs (e.g., -OMe) on the anionic ring of the pbpy ligand (substituted sites denoted as R-2 or R-3) and/or (ii) installing electron-donating substituents (e.g., -H, -Me, -OMe) para to the amine of the TPA group (i.e., R-1). The first oxidation potential is localized to the TPA unit when, for example, EDGs are placed at R-1 with EWGs at R-2 (e.g., the TPA(center dot+)/TPA(0) and Ru-III/Ru-II redox couples appear at +0.98 and +1.27 V vs NHE, respectively, when R-1 = -OMe and R-2 = -CF3). This situation is reversed when R-3 = EDG and R-1 = -H: TPA-based and metal-centered oxidation waves occur at +1.20 and +1.11 V vs NHE, respectively. The UV-vis spectrum for each complex is broad (e.g., absorption bands are extended from the UV region to beyond 800 nm in all cases) and intense (e.g., epsilon similar to 10(4) M-1 . cm(-1)) because of the overlapping intraligand charge-transfer and metal-to-ligand charge-transfer transitions. The information derived from this study offers guiding principles for modulating the physicochemical properties of bichromic cyclometalated ruthenium(II) complexes.

  DOI：

  10.1021/ic1025679
• 作为产物：
  描述：

  1-(2-phenyl-2-oxoethyl)pyridinium iodide 、 (E)-3-(5-bromothiophen-2-yl)-1-(pyridin-2-yl)prop-2-en-1-one 在 ammonium acetate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 14.0h， 生成 4-(5-bromothiophen-2-yl)-6-phenyl-2,2'-bipyridine
  参考文献：
  名称：

  Systematic Modulation of a Bichromic Cyclometalated Ruthenium(II) Scaffold Bearing a Redox-Active Triphenylamine Constituent

  摘要：

  The syntheses and physicochemical properties of nine bis-tridentate ruthenium(II) complexes containing one cyclometalating ligand furnished with terminal triphenylamine (TPA) substituents are reported. The structure of each complex conforms to a molecular scaffold formulated as [Ru-II(TPA-2,5-thiophene-pbpy)(Me(3)tctpy)] (pbpy = 6-phenyl-2,2'-bipyridine; Me(3)tctpy = trimethyl-4,4',4 ''-tricarboxylate-2,2':6',2 ''-terpyridine), where various electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) are installed about the TPA unit and the anionic ring of the pbpy ligand. It is found that the redox chemistry of the Ru center and the TPA unit can be independently modulated by (i) placing EWGs (e.g., -CF3) or EDGs (e.g., -OMe) on the anionic ring of the pbpy ligand (substituted sites denoted as R-2 or R-3) and/or (ii) installing electron-donating substituents (e.g., -H, -Me, -OMe) para to the amine of the TPA group (i.e., R-1). The first oxidation potential is localized to the TPA unit when, for example, EDGs are placed at R-1 with EWGs at R-2 (e.g., the TPA(center dot+)/TPA(0) and Ru-III/Ru-II redox couples appear at +0.98 and +1.27 V vs NHE, respectively, when R-1 = -OMe and R-2 = -CF3). This situation is reversed when R-3 = EDG and R-1 = -H: TPA-based and metal-centered oxidation waves occur at +1.20 and +1.11 V vs NHE, respectively. The UV-vis spectrum for each complex is broad (e.g., absorption bands are extended from the UV region to beyond 800 nm in all cases) and intense (e.g., epsilon similar to 10(4) M-1 . cm(-1)) because of the overlapping intraligand charge-transfer and metal-to-ligand charge-transfer transitions. The information derived from this study offers guiding principles for modulating the physicochemical properties of bichromic cyclometalated ruthenium(II) complexes.

  DOI：

  10.1021/ic1025679

文献信息

• Derivatization of Bichromic Cyclometalated Ru(II) Complexes with Hydrophobic Substituents
  作者：Kiyoshi C. D. Robson、Bryan D. Koivisto、Curtis P. Berlinguette

  DOI：10.1021/ic201768e

  日期：2012.2.6

  The syntheses and physical properties of cyclometalated Ru(II) complexes containing a triphenylamine (TPA) unit bearing aliphatic groups are reported. Each member of the series consists of an octahedral Ru(II) center coordinated by a tridentate polypyridyl ligand and a tridentate cyclometalating ligand. One of the chelating ligands contains electron-deficient methyl ester groups, while a TPA unit is attached to the central ring of the adjacent chelating ligand through a thiophene bridge. This study builds on our previous work (Inorg. Chem. 2011, 50, 6019-6028; Inorg. Chem. 2011, SO, 5494-5508) by (i) outlining a synthetic protocol for installing aliphatic groups on the TPA substituents, (ii) examining the role that terminal -O-hexyl and S-hexyl groups situated on the TPA have on the electrochemical properties, and (iii) demonstrating the potential benefit of installing the TPA on the neutral chelating ligand rather than the anionic chelating ligand. The results reported herein provide important synthetic advances for our broader goal of developing bis-tridentate cyclometalated Ru(II) complexes for light-harvesting applications.