2,5,8-trithia<9>-o-benzenophane | 129540-31-4

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 2,5,8-trithia<9>-o-benzenophane
• 英文别名: 2,5,8-trithia-(9)-o-benzenophane；2,5,8-trithia[9]-o-benzenophane；2,5,8-trithia[9]orthocyclophane；2,5,8-trithia{9}-o-benzenophane；2,5,8-trithia[9]-o-cyclophane；2,5,8-trithia-o-cyclophane；3,6,9-Trithiabicyclo[9.4.0]pentadeca-1(11),12,14-triene；3,6,9-trithiabicyclo[9.4.0]pentadeca-1(15),11,13-triene
• CAS: 129540-31-4
• 化学式: C₁₂H₁₆S₃
• 分子量: 256.457
• InChiKey: PZTJAYZCFLLQSL-UHFFFAOYSA-N

物化性质

• 沸点：
  431.6±45.0 °C(Predicted)
• 密度：
  1.148±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  75.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,5,8-trithia<9>-o-benzenophane 以 乙腈 为溶剂， 生成 {Cu(P(C6H5)2CH3)(2,5,8-trithia{9}-o-benzenophane)}{ClO4}
  参考文献：
  名称：

  De Groot, Broer; Giesbrecht, Garth R.; Loeb, Stephen J., Inorganic Chemistry, 1991, vol. 30, # 2, p. 177 - 182

  摘要：

  DOI：
• 作为产物：
  描述：

  末端脱氧核苷酸转移酶 、 1,2-二(溴甲基)苯 在 硼酸三异丙酯 、 sodium methylate 、 aluminum isopropoxide 作用下， 生成 2,5,8-trithia<9>-o-benzenophane
  参考文献：
  名称：

  Edema, Jilles J. H.; Stock, H. Thijs; Buter, Jan, Angewandte Chemie, 1993, vol. 105, # 3, p. 448 - 451

  摘要：

  DOI：

文献信息

• Synthesis, spectroscopic and EXAFS studies of vanadium complexes of trithioether ligands and crystal structures of [VCl3([9]aneS3)] and [VI2(thf )([9]aneS3)] ([9]aneS3 = 1,4,7-trithiacyclononane)
  作者：Sian C. Davies、Marcus C. Durrant、David L. Hughes、Christine Le Floc’h、Simon J. A. Pope、Gillian Reid、Raymond L. Richards、J. Roger Sanders

  DOI：10.1039/a802404i

  日期：——

  A series of vanadium-(II), -(III) and -(IV) macrocyclic thioether complexes has been synthesized and characterised by analytical, magnetic and spectroscopic methods. The new complexes reported are [V([9]aneS3)}2(µ-Cl)3]Cl ([9]aneS3 = 1,4,7-trithiacyclononane), [VI2(thf)([9]aneS3)], [VI2(ttob)] (ttob = 2,5,8-trithia[9]-o-benzenophane), [VX3([9]aneS3)] (X = Cl, Br or I), [VX3([10]aneS3)] ([10]aneS3 = 1,4,7-trithiacyclodecane), [VCl3(ttob)], [VCl3([16]aneS4)] ([16]aneS4 = 1,5,9,13-tetrathiacyclohexadecane), [(VX3)2(µ-[18]aneS6)] (X = Cl or Br, [18]aneS6 = 1,4,7,10,13,16-hexathiacyclooctadecane) and [VOCl2(ttob)]. The crystal structures of [VI2(thf)([9]aneS3)] and [VCl3([9]aneS3)] and EXAFS structural data for [VX3([9]aneS3)] and [VX3([10]aneS3)] are presented and discussed. The acyclic trithioether complexes [VX3MeC(CH2SMe)3}] (X = Cl or Br) and the complex [VI2(py)4] are also reported.

  合成了一系列钒-(II)、-(III)和-(IV)宏环硫醚配合物，并通过分析、磁性和光谱方法进行了表征。报道的新配合物包括 [V([9]aneS3)}2(µ-Cl)3]Cl ([9]aneS3 = 1,4,7-三硫环壬烷)、[VI2(thf)([9]aneS3)]、[VI2(ttob)]（ttob = 2,5,8-三硫[9]-o-苯环）、[VX3([9]aneS3)]（X = Cl、Br或I）、[VX3([10]aneS3)] ([10]aneS3 = 1,4,7-三硫环十烷)、[VCl3(ttob)]、[VCl3([16]aneS4)] ([16]aneS4 = 1,5,9,13-四硫环十六烷)、[(VX3)2(µ-[18]aneS6)]（X = Cl或Br，[18]aneS6 = 1,4,7,10,13,16-六硫环十八烷）和[VOCl2(ttob)]。提供并讨论了[VI2(thf)([9]aneS3)]和[VCl3([9]aneS3)]的晶体结构，以及[ 在VX3([9]aneS3)]和[VX3([10]aneS3)]的EXAFS结构数据。此外，还报道了非环状三硫醚配合物[ VX3MeC(CH2SMe)3}]（X = Cl或Br）和配合物[VI2(py)4]。
• 1,4,7-Trithiacyclononane ([9]aneS3) and 2,5,8-trithia[9]orthocyclophane complexes of molybdenum(II) and tungsten(II): crystal structures of [WI(CO)3([9]aneS3)][BPh4] and [WI2(CO)3(NCMe)(PPh3)]
  作者：Paul K. Baker、Simon J. Coles、Marcus C. Durrant、Sharman D. Harris、David L. Hughes、Michael B. Hursthouse、Raymond L. Richards

  DOI：10.1039/dt9960004003

  日期：——

  Reaction of [MI2(CO)3(NCMe)2](M = Mo or W) with a slight excess of 1,4,7-trithiacyclonoane ([9]aneS3) in CH2Cl2 at room temperature gave the cationic complexes [MI(CO)3([9]aneS3)]I 1 and 2 in high yield. Treatment of 1 and 2 with an excess of Na[BPh4] in methanol gave [MI(CO)3([9]aneS3)][BPh4]3 and 4. The molecular structure of [WI(CO)3([9]aneS3)][BPh4]4 has been determined by X-ray crystallography. It shows that the geometry around the tungsten centre is distorted capped octahedral with a capping carbonyl ligand. Room-temperature 13C NMR studies on complexes 1 and 2 indicate a unique CO ligand, demonstrating that their structures in solution are similar to that found for 4 in the solid state. Reaction of [MI2(CO)3(NCMe)L][M = Mo or W, L = PPh3; M = W, L = P(OPh)3] with an equimolar quantity of [9]aneS3 gave the seven-co-ordinate cation/anion complexes [MI(CO)2L([9]aneS3)][MI3(CO)4]5–7. Treatment of [MI2(CO)3(NCMe)2] with 1 equivalent of 2,5,8-trithia[9]orthocyclophane (ttoc) in CH2Cl2 at room temperature gave the dicarbonylmolybdenum complex [MoI2(CO)2(ttoc)]8 or the seven-co-ordinate cation/anion tungsten complex [WI(CO)3(ttoc)][WI3(CO)4]9. Reaction of [MI2(CO)3(NCMe)L] with an equimolar amount of ttoc gave [MI(CO)2L(ttoc)][MI3(CO)4]10–12. The complex [WI2(CO)3(NCMe)(PPh3)] was also shown to have a distorted capped-octahedral geometry by X-ray crystallography.

  室温下，[MI2(CO)3(NCMe)2]（M = Mo 或 W）与略微过量的 1,4,7-三硫杂环戊烷（[9]aneS3）在 CH2Cl2 中反应，得到阳离子络合物[MI(CO)3([9]aneS3)]I 1 和 2，产率很高。在甲醇中用过量 Na[BPh4] 处理 1 和 2，得到 [MI(CO)3([9]aneS3)][BPh4]3 和 4。X 射线晶体学确定了 [WI(CO)3([9]aneS3)][BPh4]4 的分子结构。结果表明，钨中心周围的几何结构是一个带帽羰基配体的扭曲八面体。对复合物 1 和 2 进行的室温 13C NMR 研究表明，它们具有独特的 CO 配体，这表明它们在溶液中的结构与 4 在固态中的结构相似。将[MI2(CO)3(NCMe)L][M = Mo 或 W，L = PPh3；M = W，L = P(OPh)3]与等摩尔量的[9]aneS3 反应，可得到七配位阳离子/阴离子配合物[MI(CO)2L([9]aneS3)][MI3(CO)4]5-7。室温下，在 中用 1 个当量的 2,5,8-三硫杂[9]原环烷（ttoc）处理 [MI2(CO)3(NCMe)2]，可得到二羰基钼络合物 [MoI2(CO)2(ttoc)]8 或七配位阳离子/阴离子钨络合物 [WI(CO)3(ttoc)][WI3(CO)4]9。MI2(CO)3(NCMe)L] 与等摩尔量的 ttoc 反应，得到 [MI(CO)2L(ttoc)][MI3(CO)4]10-12。X 射线晶体学研究还表明，[WI2(CO)3(NCMe)(PPh3)] 复合物具有扭曲的封顶八面体几何结构。
• Tetranuclear Ag(I) complexes with an octagonal Ag4S4 core: building large structures from small macrocycles
  作者：Hilary A. Jenkins、Stephen J. Loeb、Antoni Malats i. Riera

  DOI：10.1016/0020-1693(96)05067-0

  日期：1996.5

  bonds in a facial coordination mode to one Ag(I) ion with the central S-donor bridging to the next Ag(I) ion. This completes a pseudotetrahedral geometry and results in cyclic tetramers with a [AgS] 4 4+ octagonal core. Each structure has two symmetry related anions (BF 4 − or CF 3 SO 3 − included over the opposing faces of the large tetracationic cavity. [Ag(TT[9]OC)][BF 4 ]} 4 ·2(MeCN): C 52 H 70 B

  摘要硫醚大环TT [9] OC和Me 2 TT [9] OC与Ag +盐以1：1的比例反应产生了独特的四聚阳离子，该阳离子包含八边形[Ag 4 S 4] 4+腔。这三种聚集体[AgL] [X]} 4（X = BF 4-，L = TT [9] OC; X = CF 3 SO 3-，L = TT [9] OC ； X ＝ BF 4-，L ＝ Me 2 TT [9] OC）。在每种情况下，噻环烷配体以面部配位方式键合到一个Ag（I）离子上，而中心S供体桥接到下一个Ag（I）离子上。这样就完成了伪四面体的几何形状，并形成了具有[AgS] 4 4+八角形核的环状四聚体。每个结构都有两个对称的相关阴离子（BF 4-或CF 3 SO 3-包含在大四阳离子腔的相对表面上。[Ag（TT [9] OC）] [BF 4]} 4·2（MeCN） ：C 52 H 70 B 4 F 16 N 2 S 12，P2 1
• Thiacyclophane Complexes of Rhodium and Iridium. Synthesis, Structure, and Reactivity of [M(COD)(L)][BF4] (M = Rh, Ir; L = 2,5,8-Trithia[9]-o-cyclophane (TT[9]OC), 5-Oxa-2,8-dithia[9]-o-cyclophane (ODT[9]OC))
  作者：Hilary A. Jenkins、Stephen J. Loeb

  DOI：10.1021/om00017a047

  日期：1994.5

  The complexes [M(COD)(L)][BF4] (M = Rh, Ir; L = 2,5,8-trithia[9]-o-cyclophane (TT[9]OC), 5-oxa-2,8-dithia[91-o-cyclophane (ODT[9]OC)) were prepared in acetone by the reaction of [MCl(COD)]2 with 2 equiv each of AgBF4 and L. [Rh(COD)(TT[9]OC)][BF4] (1) crystallized in the space group Pca2(1) with a = 23.951(4) angstrom, b = 8.845(2) angstrom, c = 10.463(8) angstrom, V = 2217(1) angstrom3, and Z = 4. The structure was refined to R = 5.26% and R(w) = 5.70% for 1192 reflections with F(o)2 > 3sigma(F(o)2). [Ir(COD)(TT[9]OC)] [BF4] (2) crystallized in space group P1BAR with a = 11.085(6) angstrom, b = 12.649(2) angstrom, c = 7.965(2) angstrom, alpha = 103.10(l)-degrees; beta = 93.93(1)-degrees; gamma = 89.45(1)-degrees, V = 1085.2(5) angstrom3, and Z = 2. The structure was refined to R = 4.06% and R(w) = 4.41% for 2935 reflections with F(o)2 > 3sigma(F(o)2). 1 and 2 have trigonal bipyramidal geometry with the benzylic S atoms and an olefinic bond occupying the equatorial sites and the central S atom and the other olefinic bond in the axial positions. (Rh(COD)(ODT[9]OC)][BF4](3) crystallized in the space group P2(1)/c with a = 9.173(2) angstrom, b = 24.173(6) angstrom, c = 9.907(3) angstrom, beta = 94.14(3)-degrees; V = 2190(2) angstrom3, and Z = 4. The structure refined to R = 5.84 % and R(w) = 6.87% for 2312 reflections with F(o)2 > 3sigma(F(o)2). [Tr(COD)(ODT[9]OC)][BF4] (4) crystallized in the space group P1BAR with a = 9.677(3) angstrom, b = 13.142(6) angstrom, c = 8.996(2) angstrom, alpha = 107.48(3)-degrees; beta = 92.87(3)-degrees; gamma = 97.46(3)-degrees, V = 1077.2(7) angstrom3, and Z = 2. The structure was refined to R = 7.38% and R(w) = 6.59% for 3802 reflections with F(o)2 > 3sigma(F(o)2). 3 and 4 are square planar complexes with the benzylic S atoms and olefinic bonds coordinated. Reaction of 1 with CO yielded the complexes [Rh(CO)2(TT[9]OC)][BF4] (5) and [(TT[9]OC)Rh(mu-CO)3Rh(TT[9]OC)][BF4]2 (6). 2 was relatively unreactive toward CO; however, reactions with [IrCl(COE)2]2 yielded [lr(COE)(CO)(TT[9]OC)][BF4] (7) and [Ir(CO)2(TT[9]OC)][BF4] (8) upon reaction with TT[9]OC and CO. [lr(COE)(CO)(TT[9]OC][BF4] (7) crystallized in the space group Pbca with a = 23.338(5) angstrom, b = 24.646(9) angstrom, c = 13.805(5) angstrom, V = 7940(4) angstrom3 , and Z = 8. The structure was refined to R = 7.68 % and R(w) = 7.98% for 1493 reflections with F(o)2 > 3sigma(F(o)2). 7 has trigonal bipyramidal geometry similar to 2 with the CO group in an axial position. 3 and 4 reacted with CO to yield [Rh(CO)3(ODT[9]OC)][BF4] (9) and [Ir(CO)3(ODT[9]OC)][BF4] (10), respectively. Reactions of 1-4 with NOBF4 yielded the adducts [M(NO)(COD)(L)][BF4]2(11-14). [Ir(NO)(COD)(ODT[9]OC)][BF4]2(14) crystallized in the space group Pnma with a = 18.821(6) angstrom, b = 9.611(5) angstrom, c = 14.225(8) angstrom, v = 2573(2) angstrom3, and Z = 4. The structure was refined to R = 5.11% and R(w) = 4.83% for 1180 reflections with F(o)2 > 3sigma(F(o)2). 14 has square pyramidal geometry with the bent NO group in an apical position.
• Boric acid mediated preparation of mesocyclic thiocrown ethers containing xylylene units. Molecular structures of 3,8-dibenzo-1,6-di-thiacyclodecane and 2,5,8-trithia-(9)-p-benzenophane
  作者：Jilles J.H Edema、H.Thijs Stock、Jan Buter、Richard M Kellogg、Wilberth J.J Smeets、Anthony L Spek

  DOI：10.1016/s0040-4020(01)85752-5

  日期：1993.1

  Reaction of a dithiol with B(OH)3 and base in MeOH followed by reaction with xylylene dibromides proceeds selectively to give the corresponding ortho, meta or para-cyclophanes in good yield (70-86 %). The syntheses of examples of all three types of benzenophanes are discussed. The molecular structures of 3,8-dibenzo-1,6-dithiacyclodecane (8) and 2,5,8-trithia-(9)-p-benzenophane (5) have been determined by X-ray crystallography. Crystal data for 8: space group P2(1)/c with a=8.2745(10), b=4.9330(10), c=16.5500(12) A, beta=100.37 (1)-degrees, Z=2; R=0.043 (R(w)=0.045) for 949 reflections (I>2.5 sigma (I)). Crystal data for 5 (150K): Space group P2(1)/c with a=10.310(1), b=7.430 (1), c=17.681(2) A, beta=113.27(1)-degrees, Z=4; R=0.065 (R(w)=0.065) for 1969 reflections (I>2.5 sigma(I)).