2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane | 183310-21-6

• 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: 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane
• 英文别名: 3,6,9-Trithia-20,23-diazatetracyclo[9.8.4.014,22.017,21]tricosa-1(20),11(23),12,14(22),15,17(21),18-heptaene
• CAS: 183310-21-6
• 化学式: C₁₈H₁₈N₂S₃
• 分子量: 358.552
• InChiKey: CGMVDKKCCBQKLG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  102
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane 以 乙醚 、 水 、 乙腈 为溶剂， 生成 [Ni(2,5,8-trithia[9],(2,9)-1,10-phenanthrolinophane)(acetonitrile)][BF4]2
  参考文献：
  名称：

  Blake, Alexander J.; Demartin, Francesco; Devillanova, Francesco A., Journal of the Chemical Society, Dalton Transactions, 1996, # 18, p. 3705 - 3712

  摘要：

  DOI：
• 作为产物：
  描述：

  1,10-菲啰啉-2,9-二甲醛 在 sodium tetrahydroborate 、 氯化亚砜 、 caesium carbonate 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 10.0h， 生成 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane
  参考文献：
  名称：

  用含1,10-菲咯啉亚基的硫醚冠官能化的 Re（i）衍生物，作为一类新的化学传感器†

  摘要：

  已经合成了一系列发光的fac- [Re（CO）3（L）（NN）] +配合物，其中L是吡啶或咪唑，NN是混合的供体五齿硫醚冠的1,10-菲咯啉亚基，并且已经分析了它们的发光特性。然后，杂金属Re（I）/ Au（I）配合物，其中Au（I）片段直接键合到咪唑配体上；杂金属Re（I）/ Ag（I）配合物，其中银片段配位S-供体环的硫醚连接基也已制备。对它们的发光特性的分析表明，Re（I）/ Ag（I）衍生物，在银中心与大环单元脂族链的S-供体原子配位时。

  DOI：

  10.1039/c5dt02723c

文献信息

• Mixed aza–thia crowns containing the 1,10-phenanthroline sub-unit. Substitution reactions in [NiL(MeCN)][BF4]2 {L = 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane} †
  作者：Alexander J. Blake、Jaume Casabò、Francesco A. Devillanova、Lluis Escriche、Alessandra Garau、Francesco Isaia、Vito Lippolis、Raikko Kivekas、Vincens Muns、Martin Schröder、Reijo Sillanpää、Gaetano Verani

  DOI：10.1039/a808062c

  日期：——

  The substitution reactions of the co-ordinated acetonitrile molecule in [NiL(MeCN)][BF4]2 1 (L = 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane) with different anionic and neutral ligands L′ [Cl–, Br–, I–, CN–, SCN–, H2O, pyridine (py), aniline (an), 1,3-dimethyl-4-imidazoline-2-thione (etu) or 1,3-dimethyl-4-imidazoline-2-selone (eseu)] have been studied by using electronic spectroscopy. While the reaction with all the anionic ligands is quantitative, for the neutral ones an equilibrium takes place; the corresponding equilibrium constants have been determined in MeCN at 25 °C. The complex cations [NiL(L′)](2 – n)+ (n = 0 for neutral and 1 for anionic ligands) have also been isolated in the solid state, mainly as BF4– salts and the compounds [NiL(H2O)][ClO4]2·H2O, [NiL(Cl)]Cl·H2O, [NiL(SCN)]BF4·MeNO2, [NiL(eseu)][BF4]2 and [NiL(py)][BF4]2 have been characterized by X-ray diffraction studies. In these complexes a distorted octahedral geometry is achieved at the NiII with five sites occupied by the macrocyclic ligand L and the sixth by the appropriate ligand L′. The electrochemistry of all the prepared compounds has been studied by cyclic voltammetry. In particular the reductive cyclic voltammetry of 1 in acetonitrile shows a quasi-reversible one-electron reduction wave near 1E½ = –1.0 V vs. Fc/Fc+. Electrochemical reduction by controlled-potential electrolysis at this potential in the presence of the axial ligand PMe3 and investigation of the reduced product by ESR spectroscopy confirm the reduction process to be metal based and to correspond to the formation of the [NiIL]+ species.

  配位的乙腈分子在 [NiL(MeCN)][ ]2 1（L = 2,5,8-三硫[9](2,9)-1,10-菲咯啉酚）与不同阴离子和中性配体 L' [Cl–, Br–, I–, CN–, SCN–, H2O, 吡啶（py）,苯胺（an）, 1,3-二甲基-4-咪唑啉-2-硫酮（etu）或 1,3-二甲基-4-咪唑啉-2-硒酮（eseu）] 的取代反应已被电子光谱学研究。所有阴离子配体的反应都是定量的，而对于中性配体则发生平衡；相应的平衡常数已在 MeCN 中 25 °C 下确定。配合阳离子 [NiL(L')](2–n)+（n = 0 中性配体，n = 1 阴离子配体）也在固态中分离，主要为 BF4– 盐，且化合物 [NiL( )][ClO4]2· 、[NiL(Cl)]Cl· 、[NiL(SCN)] ·MeNO2、[NiL(eseu)][ ]2 和 [NiL(py)][ ]2 已被 X 射线衍射研究表征。在这些配合物中，NiII 获得了一个扭曲的八面体几何结构，五个位点被大环配体 L 占据，第六个位点被适当的配体 L' 占据。所有制备的化合物已经通过循环伏安法研究了电化学性质。特别是 1 在乙腈中的还原循环伏安法显示出在 1E½ = –1.0 V（相对于 Fc/Fc+）附近的一个准可逆单电子还原波。在这个电位下的恒电位电解中的电化学还原以及通过 ESR 光谱对还原产物的研究证实了还原过程是以金属为基础的，并且对应于 [NiIL]+ 物种的形成。
• Conformationally locked pentadentate macrocycles containing the 1,10-phenanthroline unit. Synthesis and crystal structure of 5-oxa-2,8-dithia[9](2,9)-1,10-phenanthrolinophane (L) and its coordination properties to NiII, PdII, PtII, RhIII and RuII †
  作者：Massimiliano Arca、Alexander J. Blake、Jaume Casabò、Francesco Demartin、Francesco A. Devillanova、Alessandra Garau、Francesco Isaia、Vito Lippolis、Raikko Kivekas、Vicent Muns、Martin Schröder、Gaetano Verani

  DOI：10.1039/b100493j

  日期：——

  The complexation of the new mixed thia–aza–oxa macrocycle 5-oxa-2,8-dithia[9](2,9)-1,10-phenanthrolinophane (L) containing the 1,10-phenanthroline unit with NiII, PdII, PtII, RhIII and RuII has been investigated. The results have been compared with those obtained with the structurally related ligand 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane (L′). The most stable conformations of both ligands have been calculated in order to understand their change upon metal complexation and for L good agreement has been found with the conformations observed in the crystal structure of L·½H2O. The single-crystal structures of [Ni(L)Cl]BF4 and [Ru(L)(PPh3)][PF6]2·1//4MeCN reveal a N2S2O coordination sphere about NiII and RuII, with the macrocyclic ligand in a folded conformation and with the sixth coordination site taken up by Cl− or PPh3, respectively. For [Pd(L)][BF4]2 an [N2S2 + O] coordination is observed, with the O-donor interacting weakly with the metal centre at the apical position of a square-based coordination sphere. 13C and 1H NMR spectroscopic studies indicate that the complexes are not fluxional in solution, with the ligand imposing the same coordination sphere as observed in the solid state. 13C NMR spectroscopy has also helped in elucidating the stereochemistry of [Rh(L)Cl2]BF4 for which no suitable crystals could be grown: the two Cl− ligands are mutually trans with the N2S2 donor set of the macrocyclic ligand occupying the equatorial positions of an octahedral coordination sphere and with the O-donor atom left un-coordinated. The redox properties of all the complexes in MeCN have been studied.

  含有 1,10-菲咯啉单元的新型混合硫杂-氮杂-氧杂大环 5-oxa-2,8-二硫杂[9](2,9)-1,10-菲咯啉 (L) 与 NiII、PdII 的络合、PtII、RhIII 和 RuII 已被研究。结果与结构相关配体 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane (L') 获得的结果进行了比较。计算了两种配体最稳定的构象，以了解它们在金属络合时的变化，并且发现 L 与 L·½H2O 晶体结构中观察到的构象具有良好的一致性。 [Ni(L)Cl]BF4和[Ru(L)(PPh3)][PF6]2·1//4MeCN的单晶结构揭示了围绕NiII和RuII的N2S2O配位球，其中大环配体处于折叠状态构象和第六配位点分别由 Cl− 或 PPh3 占据。对于 [Pd(L)][BF4]2，观察到 [N2S2 + O] 配位，O 供体与方形配位球顶端位置的金属中心相互作用较弱。 13C 和 1H NMR 光谱研究表明，配合物在溶液中不流动，配体施加与固态中观察到的相同的配位球。 13C NMR 光谱还有助于阐明 [Rh(L)Cl2]BF4 的立体化学，但无法生长合适的晶体：两个 Cl− 配体与占据赤道位置的大环配体的 N2S2 供体组相互反式。八面体配位球且 O 供体原子未配位。研究了 MeCN 中所有配合物的氧化还原性质。
• Iron(<scp>ii</scp>)-induced cycloisomerization of alkynes <i>via</i> “non-vinylidene” pathways for iron(<scp>ii</scp>)-indolizine and -indolizinone complexes
  作者：Siu-Chung Chan、Chi-Fung Yeung、Hau-Lam Shek、Sze-Wing Ng、Sheung-Ying Tse、Man-Kit Tse、Shek-Man Yiu、Chun-Yuen Wong

  DOI：10.1039/d0cc05081d

  日期：——

  pyridine-functionalized alkynes and an Fe(II) precursor supported by 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane afforded the first Fe(II)-indolizine and -indolizinone complexes. Structural analysis and theoretical calculations revealed the existence of unconventional “non-vinylidene” pathways and challenged the generality of vinylidene intermediacy in Fe(II)-induced alkyne transformations.

  吡啶官能化的炔烃与由2,5,8-三硫杂[9]（2,9）-1,10-菲咯啉酮支撑的Fe（II）前体之间的反应提供了第一个Fe（II）-吲哚嗪和-吲哚嗪酮配合物。结构分析和理论计算揭示了非常规“非亚乙烯基”途径的存在，并挑战了Fe（II）诱导的炔烃转化中亚乙烯基中间体的普遍性。
• Coordination Chemistry of 2,5,8-Trithia[9],(2,9)-1,10-phenanthrolinophane (L) toward Rhodium(III) at the Polarised Water/1,2-Dichloroethane Interface − A Possible New Approach to the Problem of Separating RhIII from Chloride Media
  作者：Alexander J. Blake、M. Helena M. Caçote、Francesco A. Devillanova、Alessandra Garau、Francesco Isaia、Vito Lippolis、Carlos M. Pereira、Fernando Silva、Lorenzo Tei

  DOI：10.1002/1099-0682(200207)2002:7<1816::aid-ejic1816>3.0.co;2-y

  日期：2002.7
• Complexes of CuII with mixed-donor phenanthroline-containing macrocycles: analysis of their structural, redox and spectral properties in the context of Type-1 blue copper proteins biomimetic models
  作者：Massimiliano Arca、Gholamhassan Azimi、Francesco Demartin、Francesco A. Devillanova、Lluis Escriche、Alessandra Garau、Francesco Isaia、Raikko Kivekas、Vito Lippolis、Vicent Muns、Alessandro Perra、Mojtaba Shamsipur、Luigi Sportelli、Abdollah Yari

  DOI：10.1016/j.ica.2005.01.014

  日期：2005.4

  The macrocycles L-1-L-3 having N2S2O-, N2S2-, and N2S3-donor sets, respectively, and incorporating the 1,10-phenanthroline unit interact in EtOH and MeCN solutions with Cu-II to give 1:1 [M(L)](2+) complex species. The compounds [Cu(L-1)(ClO4)]ClO4 (1), [Cu(L-2)(ClO4)]ClO4 center dot 1/2H(2)O (2) and [Cu(L-3)](ClO4)(2) (3) were isolated at the solid state and the first two also characterised by X-ray diffraction studies. The conformation adopted by L-1 and L 2 in the cation complexes reveals the aliphatic portion of the rings folded over the plane containing the heteroaromatic moiety with the ligands encapsulating the metal centre within their cavity by imposing. respectively, a square-based pyramidal and a square planar geometry. In both complexes, the metal ion completes its coordination sphere by interacting with a ClO4- ligand. The compound [Cu(L-3)(2)](PF6)(2) (4) containing a 1:2 cation complex was also isolated at the solid state: EPR spectroscopy measurements suggest the presence of a CuN4 chromophore in this complex. The EPR and electronic spectral features of 1-4 have been studied and their redox properties examined in comparison with those observed for Type-1 blue copper proteins.The reactivity of L-1-L-3 has also been tested toward stoichiometric amounts of the Cut salt [CuCl(PPh3)(3)], (c) 2005 Elsevier B.V. All rights reserved.