(1,4,7,10,13,16-hexathiacyclooctadecane)silver(I) perchlorate | 77424-48-7

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机含氧阴离子化合物
• 英文名称: (1,4,7,10,13,16-hexathiacyclooctadecane)silver(I) perchlorate
• CAS: 77424-48-7
• 化学式: C₁₂H₂₄AgS₆*ClO₄
• 分子量: 568.037
• InChiKey: SNTPTFXCWWCFPP-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为产物：
  描述：

  六硫环辛烷 、 silver perchlorate 以 乙醇 、 丙酮 为溶剂， 生成 (1,4,7,10,13,16-hexathiacyclooctadecane)silver(I) perchlorate
  参考文献：
  名称：

  大环聚硫醚作为溶剂萃取剂—IV Ag（I）和Hg（II）与1,4,7,10,13,16-六硫代环十八烷的配合物

  摘要：

  研究了由Ag（I）和Hg（II）与大环聚硫醚1,4,7,10,13,16-六硫代环十八烷（HTO）形成的配合物。对应于通式[AgClO 4 ] n ·HTO（分别为n，1、2、3），[AgBF 4 ] 2 ·HTO，HgCl 2 ·HTO，[HgCl 2 ] 2 ·HTO，Hg（ClO 4）的配合物）2 ·HTO，Hg（BF 4）2 ·HTO和[Hg（CH 3 COO）2 ] 2·HTO已被分离和表征。根据电导率数据，Hg（II）氯化物，乙酸盐和氟硼酸盐络合物是非电解质。AgClO 4 ·HTO，[AgBF 4 ] 2 ·HTO和[AgClO 4 ] 2 ·HTO的络合物是硝基苯中的1：1电解质。红外光谱表明汞和高氯酸银配合物中键合的离子特性。已经研究了从氯化物和高氯酸盐水溶液中溶剂萃取金属的方法。

  DOI：

  10.1016/0022-1902(81)80452-6

文献信息

• Redox Non-innocence of Thioether Macrocycles:  Elucidation of the Electronic Structures of Mononuclear Complexes of Gold(II) and Silver(II)
  作者：Jennifer L. Shaw、Joanna Wolowska、David Collison、Judith A. K. Howard、Eric J. L. McInnes、Jonathan McMaster、Alexander J. Blake、Claire Wilson、Martin Schröder

  DOI：10.1021/ja0636439

  日期：2006.10.1

  The mononuclear +2 oxidation state metal complexes [Au([9]aneS(3))(2)](2+) and [Ag([18]aneS(6))](2+) have been synthesized and characterized crystallographically. The crystal structure of the Au(II) species [Au([9] aneS(3))(2)](BF4)(2) shows a Jahn-Teller tetragonally distorted geometry with Au-S(1) = 2.839(5), Au-S(2) = 2.462(5), and Au-S(3) = 2.452(5) angstrom. The related Ag(II) complex [Ag([18] aneS(6))](ClO4)(2) has been structurally characterized at both 150 and 30 K and is the first structurally characterized complex of Ag(II) with homoleptic thioether S-coordination. The single-crystal X-ray structure of [Ag([18]aneS(6))](ClO4)(2) confirms octahedral homoleptic S-6-thioether coordination. At 150 K, the structure contains two independent Ag(II)-S distances of 2.569(7) and 2.720(6) angstrom. At 30 K, the structure retains two independent Ag(II)-S distances of 2.615(6) and 2.620(6) angstrom, with the complex cation retaining 3-fold symmetry. The electronic structures of [Au([9]aneS(3))(2)](2+) and [Ag([18]aneS(6))](2+) have been probed in depth using multifrequency EPR spectroscopy coupled with DFT calculations. For [Au([9] aneS(3))(2)](2+), the spectra are complex due to large quadrupole coupling to Au-197. Simulation of the multifrequency spectra gives the principal g values, hyperfine (A) and quadrupole (P) couplings, and furthermore reveals non-co-incidence of the principal axes of the P tensor with respect to the A and g matrices. These results are rationalized in terms of the electronic and geometric structure and reveal that the SOMO has ca. 30% Au 5d(xy) character, consistent with DFT calculations (27% Au character). For [Ag([18]aneS(6))](2+), detailed EPR spectroscopic analysis confirms that the SOMO has ca. 26% Ag 4d(xy) character and DFT calculations are consistent with this result (22% Ag character).