1,5-diselena-9,13-dithiacyclohexadecane | 278796-27-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 有机二硫化物
• 英文名称: 1,5-diselena-9,13-dithiacyclohexadecane
• 英文别名: 1,5-Dithia-9,13-diselenacyclohexadecane
• CAS: 278796-27-3
• 化学式: C₁₂H₂₄S₂Se₂
• 分子量: 390.375
• InChiKey: WKNXGFXPAWDZAA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.11
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  50.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1,5-diselena-9,13-dithiacyclohexadecane 、 (1,5-diselena-9,13-dithiacyclohexadecane)copper(II) trifluoromethanesulfonate 以 二氯甲烷 为溶剂， 生成 (1,5-diselena-9,13-dithiacyclohexadecane)copper(I) trifluoromethanesulfonate
  参考文献：
  名称：

  新硒化钴和硒化铜（I）和铜（II）配合物的合成，表征和氧化还原行为。

  摘要：

  The synthesis and characterization of new selenium coronands and of copper(I) and copper(II) complexes of selenium coronands are reported. Molecular structures in the solid state have been determined by X-ray crystallography. The molecular structures of 6,7,13,14-dibenzo-1,5,8,12-tetraselenacy (dibenzo-14Se4 (1)) and 1,5,9-triselenacyclododecane (12Se3 (2)) adopt conformations which maximize the number of possible gauche C-Se-C-C bond torsion angles. 1: T = 190 K; orthorhombic, space group Pca2(1); fw = 552.19; Z = 4; a = 9.645(3) Angstrom; b = 12.679(6) Angstrom; c 15.332(4) Angstrom; V = 1874.9 Angstrom(3); R-F = 0.027 for 1732 data (I-o greater than or equal to 2.5 sigma(I-o)) and 200 variables. 2: T = 190 K; orthorhombic, space group Pn2(1)a; fw = 363.12; Z = 4; a = 14.943(4) Angstrom, b = 5.638(2) Angstrom; c = 14.229(3) Angstrom, V = 1198.8 Angstrom(3); R-F = 4.026 for 862 data (I-o greater than or equal to 2.5 sigma(I-o)) and 111 variables. The molecular structures of 1,5-diselena-9,13-dithiacyclohexadecane (16Se2S2 (3)) and [Cu(16Se2S2)][SO3CF3](2) (4) correspond to those displayed by both of the analogous tetrathia and tetraselena macrocycles. Compound 3 adopts a [3535] quadrangular conformation. Compound 4, [Cu(16Se4(OH)2][SO3CF3](2) (5) (where 16Se4(OH)(2) = cis-1,5,9,13-tetraselenacyclohexadecane-3,11-diol), and [Cu(8Se2(OH))(2)][SO3CF3](2) (6) (where 8Se2(OH) = 1.5-diselenacyclooctan-3-ol) have typical tetragonally distorted octahedral coordination environments of Cu(II). Compounds 4 and 5 both display a c,t,c configuration of the coronand. Compound 5 has only one hydroxyl group coordinated in an axial position, which requires that the corresponding Se-Cu-Se-C-C-C ring be locked into a boat rather than a chair conformation.The hydroxyl groups in 6 occupy the axial coordination positions. 3: T = 200 K; monoclinic, space group C2/c; fw = 390.36; Z = 12; a = 24.202(9) Angstrom; b = 18.005(7) Angstrom; c 16.235(5) Angstrom; beta 138.23(3)degrees; V = 4713 Angstrom(3); R-F = 0.052 for 1881 data (I-o greater than or equal to 2.5 sigma(I-o)) and 172 variables. 4: T = 297 K: monoclinic, space group P2(1)/n; fw = 752.03; Z = 2; a = 8.882(2) Angstrom; b = 10.874(2) A; c = 13.360(2) Angstrom; beta = 97.95(2)degrees; V = 1277.9 Angstrom(3); R-F = 0.028 for 1610 data (I-o greater than or equal to 2.5 sigma(I-o)) and 176 variables. 5: T = 190 K; monoclinic, space group P2(1)/n; fw = 877.84; Z = 4; a = 8.412(5) Angstrom; b = 20.924(5) Angstrom; c = 15.021(5) Angstrom; beta = 100.82(4)degrees; V = 2597 Angstrom(3); R-F = 0.059 for 2152 data (I-o greater than or equal to 2.5 sigma(I-o)) and 185 variables. 6: T = 195 K; monoclinic, space group P2(1)/c; fw = 877.84; Z = 2; a = 6.675(2) Angstrom; b = 10.945(2) Angstrom; c = 17.496(2) Angstrom, beta = 96.76(2)degrees; V = 1307.3 Angstrom(3); R-F = 0.023 for 1816 data (I-o greater than or equal to 2.5 sigma(I-o)) and 159 variables. [Cu(16Se2S2)][SO3CF3] (7) and [Cu(16Se4(OH))][SO3CF3] (8) (where 16Se4(OH) = 1,5,9,13-tetraselenacyclohexadecan-3-ol) are both terrahedral Cu(I) coronand complexes with typical t,t,t configurations.7. T = 205 K; triclinic, space group P (1) over bar; fw = 602.97; Z = 2; a = 10.512(3) Angstrom; b = 10.674(2) Angstrom; c = 10.682(3) Angstrom; alpha = 101.47(2)degrees; beta = 116.82(2)degrees; gamma = 93.59(2)degrees; V = 1032.3 Angstrom(3); R-F = 0.029 for 2237 data (I-o greater than or equal to 2.5 sigma(I-o)) and 264 variables. 8: T = 297 K; monoclinic, space group P2(1)/n; fw = 712.77; Z = 4; a = 13.695(2) Angstrom; b = 11.202(2) Angstrom; c = 14.163(3) Angstrom; beta = 92.35(2)degrees; V = 2170.9 Angstrom(3); R-F = 0.035 for 2086 data (I-o greater than or equal to 2.5 sigma(I-o)) and 189 variables. Compounds 5, 6, and 8 all display hydrogen bonding between hydroxyl groups and the SO3CF3- ions. Isotropic C-13 and Se-77 chemical shifts have been obtained in the solid state for 2,3,1,5,9,13-tetraselenacyclohexadecane-3, 11-diol (16Se4(OH)(2) (9)), 1,5,9,13-etraselenacyclohexadecan-3-ol (16Se4(OH) (10)), and the dicationic complex 1,5,-(diseleniacyclooctane trifluoromethanesulfonate (8Se2(SO3CF3)(2) (11)). In addition, the Se-77 chemical shift anisotropies have been determined for 10 and 11. The dicationic compound 11 resonates at lower field, reflective of a contribution from the transannular Se-Se bond. The redox behavior of 1-8 has been examined by means of cyclic voltammetry. Redox behavior of the copper complexes 4, 5, and 6 indicates the presence of two different conformational isomers of the Cu(I) complexes that are oxidized at different potentials, analogous to Rorabacher's copper(II/I) complexes that follow a dual-pathway square-scheme mechanism. The quasi-reversible cyclic voltammograms observed for the Cu(II) complexes of selenium coronands reflect the configurational changes between Cu(II) complexes (octahedral or tetragonal configurations) and Cu(T) complexes (tetrahedral configurations) and indicate that the configurational changes are slower than the electron transfers to the electrode.

  DOI：

  10.1021/ic991345p