4',5'-ethylenedithiotetrathiafulvenyl[4,5-f][1,10]phenanthroline | 1208267-06-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: 4',5'-ethylenedithiotetrathiafulvenyl[4,5-f][1,10]phenanthroline
• 英文别名: EDT-TTF-phen；2-(5,6-Dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-ylidene)-[1,3]dithiolo[4,5-f][1,10]phenanthroline；2-(5,6-dihydro-[1,3]dithiolo[4,5-b][1,4]dithiin-2-ylidene)-[1,3]dithiolo[4,5-f][1,10]phenanthroline
• CAS: 1208267-06-4
• 化学式: C₁₈H₁₀N₂S₆
• 分子量: 446.687
• InChiKey: IHBBHBWZQLWXKT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  26
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  178
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  五羰基氯铼(I) 、 4',5'-ethylenedithiotetrathiafulvenyl[4,5-f][1,10]phenanthroline 以 甲苯 为溶剂， 以78%的产率得到tricarbonylchloro(4',5'-ethylenedithiotetrathiafulvenyl[4,5-f][1,10]phenanthroline)rhenium(I)
  参考文献：
  名称：

  Syntheses, Characterization, and Properties of Rhenium(I) Tricarbonyl Complexes with Tetrathiafulvalene-Fused Phenanthroline Ligands

  摘要：

  A series of tetrathiafulvalene-annulated phenanthroline ligands, 4',5'-dimethyldithiotetrathiafulvenyl[4,5-f][1,10]phenanthroline (L-1), 4',5'-ethylenedithiotetrathiafulvenyl[4,5-f] [1,10] phenanthroline (L-2), and 4',5'-bis(methyloxycarbonyl)dithiotetrathiafulvenyl[4,5-f][1,10]phenanthroline (L-3), have been prepared by a facile and efficient synthetic procedure under mild conditions. Further coordination reactions of these ligands with Re (CO)(5) Cl afford new rhenium tricarbonyl complexes, Re(CO)(3)Cl(L) (L = L-1, 3a; L = L-2, 3b; L = L-3, 3c), respectively. X-ray crystal structure determinations on 3a,c reveal that the ligands are nearly planar and they show a unique packing mode in the solid state. The electrochemical and spectroscopic behavior of these compounds (L-1-L-3, 3a-c) has been studied. The results suggest that the redox-active tetrathiafulvalene-phenanthroline ligands are useful for new metal complexes.

  DOI：

  10.1021/om101141h
• 作为产物：
  描述：

  5,6-二溴-1,10-菲罗啉 在 mercury(II) diacetate 、 溶剂黄146 、 亚磷酸三乙酯 作用下， 以 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 51.0h， 生成 4',5'-ethylenedithiotetrathiafulvenyl[4,5-f][1,10]phenanthroline
  参考文献：
  名称：

  氧化还原活性配体的配合物：Ru（II）与TTF修饰的邻菲咯啉配合物的合成，结构以及电化学和光物理行为

  摘要：

  具有螯合配体的Ru（II）配合物，4'，5'-乙撑二硫代四硫富烯基[4,5- f ] [1,10]菲咯啉（L1），1,3-二硫代-2-硫代[4,5- f ] [制备了1,10]菲咯啉（L2）和1,3-二硫代-2-壬基[4,5- f ] [1,10]菲咯啉（L3），并对其结构，电化学和光物理性质进行了研究。密度泛函理论（DFT）计算表明[Ru（bpy）2（L1）]（PF 6）2（1）位于四硫富瓦烯（TTF）亚基上，在三个以Ru为中心的d轨道上方约0.6 eV出现。与该发现一致的是，1表现出三个可逆的氧化反应：两个较低电势发生在TTF亚基上，一个较高电势归因于Ru 3+ / Ru 2+氧化还原对。配合物[Ru（bpy）2（L2）]（PF 6）2（2）和[Ru（bpy）2（L3）]（PF 6）2（3）仅显示Ru 3+ / Ru 2+相关的氧化。所有配合物的光吸收光谱揭示了以450 nm为中心的特

  DOI：

  10.1021/ic4006949

文献信息

• 10.1021/acs.inorgchem.4c01389
  作者：Casas, Jaison、Baudron, Stéphane A.、Bonnefont, Antoine、Chaumont, Alain、Chauvin, Jérôme、Mobian, Pierre、Ruhlmann, Laurent

  DOI：10.1021/acs.inorgchem.4c01389

  日期：——

  tetrathiafulvalene (TTF) unit and a Ti(IV) center, a monomeric heteroleptic octahedral Ti(IV) complex containing a diimine ligand composed of a 1,10-phenanthroline core fused with a TTF fragment (ligand 2a) was prepared. The stable complex formulated as Ti(1)2(2a), where 1 is a 2,2′-biphenolato derivative, was efficiently synthesized by following a one-step approach. This complex and its model species [Ti(1)2(2b)]

  为了深入研究四硫富瓦烯 (TTF) 单元和 Ti(IV) 中心之间的相互作用，我们设计了一种单体杂配八面体 Ti(IV) 配合物，该配合物含有由 1,10-菲咯啉核心与 TTF 片段（配体2a）融合组成的二亚胺配体。 ）准备好了。通过一步法有效合成了稳定配合物 Ti( 1 ) 2 ( 2a )，其中1是 2,2'-联苯酚衍生物。该配合物及其模型物种[Ti( 1 ) 2 ( 2b )]在溶液中得到了充分表征，并通过单晶X射线衍射分析建立了它们的固态结构。密度泛函理论计算允许对涉及以紫外-可见吸收光谱为特征的电子跃迁的前沿轨道进行分配。电化学和光谱电化学研究表明，Ti( 1 ) 2 ( 2a )内的TTF单元可以经历两个可逆的单电子氧化过程；强调了 Ti(IV) 原子的可逆单电子还原。对这个供体-受体分子系统进行的光物理测量表明，光激发下的电子转移过程发生在Ti( 1 ) 2 ( 2a )内。
• TTF-Annulated Phenanthroline and Unexpected Oxidative Cleavage of the C═C Bond in Its Ruthenium(II) Complex
  作者：Lawrence K. Keniley、Lipika Ray、Kirill Kovnir、Logan A. Dellinger、Jordan M. Hoyt、Michael Shatruk

  DOI：10.1021/ic902230f

  日期：2010.2.15

  Tetrathiafulvalene (TTF) and 1,10-phenanthroline have been fused together via a simple and efficient synthetic procedure that provides a new bidentate ligand, 4',5'-ethylenedithiotetrathiafulvenyl[4,5-f]-[1,10]phenanthroline (EDT-TTF-phen, 1). Its ruthenium(II) complex exhibits a unique packing of TTF subunits in the solid state. In an acetonitrile solution, [Ru(bpy)(2)(1)](PF6)(2) undergoes facile oxidative cleavage of the C=C double bond, which cannot be observed in the dark or under anaerobic conditions. This points to the photocatalytic role played by the ruthenium(II) chromophore in this conversion.
• Syntheses, Characterization, and Properties of Rhenium(I) Tricarbonyl Complexes with Tetrathiafulvalene-Fused Phenanthroline Ligands
  作者：Jie Qin、Liang Hu、Gao-Nan Li、Xi-Sen Wang、Yan Xu、Jing-Lin Zuo、Xiao-Zeng You

  DOI：10.1021/om101141h

  日期：2011.4.25

  A series of tetrathiafulvalene-annulated phenanthroline ligands, 4',5'-dimethyldithiotetrathiafulvenyl[4,5-f][1,10]phenanthroline (L-1), 4',5'-ethylenedithiotetrathiafulvenyl[4,5-f] [1,10] phenanthroline (L-2), and 4',5'-bis(methyloxycarbonyl)dithiotetrathiafulvenyl[4,5-f][1,10]phenanthroline (L-3), have been prepared by a facile and efficient synthetic procedure under mild conditions. Further coordination reactions of these ligands with Re (CO)(5) Cl afford new rhenium tricarbonyl complexes, Re(CO)(3)Cl(L) (L = L-1, 3a; L = L-2, 3b; L = L-3, 3c), respectively. X-ray crystal structure determinations on 3a,c reveal that the ligands are nearly planar and they show a unique packing mode in the solid state. The electrochemical and spectroscopic behavior of these compounds (L-1-L-3, 3a-c) has been studied. The results suggest that the redox-active tetrathiafulvalene-phenanthroline ligands are useful for new metal complexes.
• Complexes with Redox-Active Ligands: Synthesis, Structure, and Electrochemical and Photophysical Behavior of the Ru(II) Complex with TTF-Annulated Phenanthroline
  作者：Lawrence K. Keniley、Nathalie Dupont、Lipika Ray、Jie Ding、Kirill Kovnir、Jordan M. Hoyt、Andreas Hauser、Michael Shatruk

  DOI：10.1021/ic4006949

  日期：2013.7.15

  of [Ru(bpy)2(L1)](PF6)2 (1) is located on the tetrathiafulvalene (TTF) subunit and appears ∼0.6 eV above the three Ru-centered d orbitals. In agreement with this finding, 1 exhibits three reversible oxidations: the two at lower potentials take place on the TTF subunit, and the one at higher potential is due to the Ru3+/Ru2+ redox couple. Complexes [Ru(bpy)2(L2)](PF6)2 (2) and [Ru(bpy)2(L3)](PF6)2 (3)

  具有螯合配体的Ru（II）配合物，4'，5'-乙撑二硫代四硫富烯基[4,5- f ] [1,10]菲咯啉（L1），1,3-二硫代-2-硫代[4,5- f ] [制备了1,10]菲咯啉（L2）和1,3-二硫代-2-壬基[4,5- f ] [1,10]菲咯啉（L3），并对其结构，电化学和光物理性质进行了研究。密度泛函理论（DFT）计算表明[Ru（bpy）2（L1）]（PF 6）2（1）位于四硫富瓦烯（TTF）亚基上，在三个以Ru为中心的d轨道上方约0.6 eV出现。与该发现一致的是，1表现出三个可逆的氧化反应：两个较低电势发生在TTF亚基上，一个较高电势归因于Ru 3+ / Ru 2+氧化还原对。配合物[Ru（bpy）2（L2）]（PF 6）2（2）和[Ru（bpy）2（L3）]（PF 6）2（3）仅显示Ru 3+ / Ru 2+相关的氧化。所有配合物的光吸收光谱揭示了以450 nm为中心的特