1,5-bis(2-mercaptoethyl)-1,5-diazacyclooctane | 129944-05-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1,5-bis(2-mercaptoethyl)-1,5-diazacyclooctane
• 英文别名: 1,5-bis(mercaptoethyl)-1,5-diazacyclooctane；N,N'-bis(2-mercaptoethyl)-1,5-diazacyclooctane；bis-mercaptoethanediazacyclooctane；H2-bme-daco；2-[5-(2-Sulfanylethyl)-1,5-diazocan-1-yl]ethanethiol
• CAS: 129944-05-4
• 化学式: C₁₀H₂₂N₂S₂
• 分子量: 234.43
• InChiKey: WSOOQVLSFOUZDD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  8.5
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,5-bis(2-mercaptoethyl)-1,5-diazacyclooctane 在 CH₃I 作用下， 以 乙腈 为溶剂， 生成
  参考文献：
  名称：

  Mills, Daniel K.; Reibenspies, Joseph H.; Darensbourg, Marcetta Y., Inorganic Chemistry, 1990, vol. 29, # 22, p. 4364 - 4366

  摘要：

  DOI：

文献信息

• Tetradentate N₂S₂ Vanadyl(IV) Coordination Complexes: Synthesis, Characterization, and Reactivity Studies
  作者：Roxanne M. Jenkins、Tiffany A. Pinder、Michelle L. Hatley、Joseph H. Reibenspies、Marcetta Y. Darensbourg

  DOI：10.1021/ic1022533

  日期：2011.3.7

  and FeII) while maintaining reactivity at the S-thiolate sites of the respective N2S2M complexes. The vanadyl ion, of interest for its pharmacological possibilities and its spin-label reporter properties for bioinorganic studies, also shows an affinity for such mixed nitrogen/sulfur-donor environments. Thus, (V≡O)2+ analogues of a well-characterized series of N2S2Ni complexes have been prepared as mimics

  多功能Ñ 2小号2四个齿配体（BME-DACO）2-，（BME-DACH）2-，和（EMA）4-已知容纳许多二价过渡金属离子（M =镍II，钯II，铂II，Pb II，Zn II，Cd II，Cu II和Fe II），同时在各个N 2 S 2的S-硫醇盐位点保持反应M配合物。钒氧离子因其药理学可能性及其在生物无机研究中的自旋标记报告基因特性而受到关注，它也显示出对这种混合氮/硫供体环境的亲和力。因此，已准备好一系列特征明确的N 2 S 2 Ni配合物的（V = O）2+类似物，作为由三肽基序的体内结合位点形成的可能的N 2 S 2（V = O）的模拟物， Cys-X-Cys。用烷基化剂探索了S-硫醇盐在这些系统中的亲核性。给出了IR [ν（VO）]，电子光谱和电子顺磁共振测量结果。（bme-DACo）（V≡O），（bme-DACHref=https://www.molaid.com/MS_77923 target="_blank">DACh）（V≡O）和[Et 4N] 2 [（EMA）（V ＝ O）
• Methylation of Tethered Thiolates in [(bme-daco)Zn]₂ and [(bme-daco)Cd]₂ as a Model of Zinc Sulfur-Methylation Proteins
  作者：Craig A. Grapperhaus、Thawatchai Tuntulani、Joseph H. Reibenspies、Marcetta Y. Darensbourg

  DOI：10.1021/ic971599f

  日期：1998.8.1

  The dimeric dithiolate complex [1,5-bis(mercaptoethyl)-1,5-diazacyclooctanato]zinc(II), [(bme-daco)Zn](2) or Zn-1, and its cadmium analogue, Cd-1, were investigated as models for the active site of zinc-dependent methylation proteins. The key issue addressed was whether alkylation of a thiolate in a relatively rigid tetradentate ligand would result in coordination of the thioether product to the metal

  二聚二硫醇盐络合物[1,5-双（巯基乙基）-1,5-二氮杂环辛基]锌（II），[（bme-daco）Zn]（2）或Zn-1，及其镉类似物Cd-1，作为锌依赖性甲基化蛋白活性位点的模型进行了研究。解决的关键问题是在相对刚性的四齿配体中硫醇盐的烷基化是否会导致硫醚产物与金属的配位。基于（1）H和（13）C NMR光谱以及对烷基化剂的相似反应性，建议新合成的镉配合物Cd-1与以前报道的Zn-1配合物同构。 X射线晶体学在固态下是二聚体（Tuntulani，T。； Reibenspies，JH； Farmer，PJ； Darensbourg，MY Inorg.Chem.1992，31，3497）。碘甲烷与热CH（3）OH / CH（3）CN中的Zn-1反应生成解离的硫醚，由伪四面体复合物中的碘化物配位取代，（Me（2）bme-daco）ZnI（2）或锌2。配合物Zn-2在三斜晶P＆onemacr中结晶。a
• Pentacoordinate (μ-Oxo)diiron(III) Thiolate Complexes and Dimeric Iron(II) Precursors
  作者：Ghezai Musie、Chia-Huei Lai、Joseph H. Reibenspies、Lloyd W. Sumner、Marcetta Y. Darensbourg

  DOI：10.1021/ic980475f

  日期：1998.8.1

  reaction of free ligand with the iron source, Fe(acac)(3), gave good yields in shorter time. With the less sterically encumbered derivative, [(bme-daco)Fe](2), the only successful route to [(bme-daco)Fe](2)O required single O-atom sources such as 4-chloropyridine N-oxide to be present during the preparation of the complex; attempted use of molecular O(2) either during the synthesis or following isolation of

  N，N'-双（2-甲基-2-巯基丙烷）-1,5-二氮杂环辛烷（H（2）bme-daco）和N，N'-bis的（＆mgr; -oxo）二铁（III）配合物（巯基乙基）-1,5-二氮杂环辛烷（H（2）bme-daco）配体在硫供体存在的情况下呈现出特征鲜明的（＆mgr--氧代）二铁（III）物种的罕见例子。分子氧与二铁（II）络合物[（bme-daco）Fe]（2）的反应可缓慢形成＆mgr-oxo物种，而O（2）在铁源Fe（acac）（3）的游离配体在较短的时间内产生了良好的收率。借助空间分布较小的衍生物[（bme-daco）Fe]（2），唯一成功获得[（bme-daco）Fe]（2）O的方法需要单个O原子源，例如4-氯吡啶N-氧化物在准备配合物时出现；尝试在合成过程中或分离出铁（II）二聚体[（bme-daco）Fe]（2）后使用分子O（2）。即，反应物[（bme-daco）Fe]（2）和产
• Bismercaptoethanediazacyclooctane as a N₂S₂ Chelating Agent and Cys−X−Cys Mimic for Fe(NO) and Fe(NO)₂
  作者：Chao-Yi Chiang、Matthew L. Miller、Joseph H. Reibenspies、Marcetta Y. Darensbourg

  DOI：10.1021/ja049627y

  日期：2004.9.1

  The N-protonated bismercaptoethanediazacyclooctane serves as a bidentate dithiolate ligand to oxidized Fe(NO)(2) of Enemark-Feltarn notation, E-F Fe(NO)(2)},(9) mimicking Cys-X-Cys binding of Fe(NO)(2) to proteins or thio-biomolecules. The neutral compound is characterized by the well-known g = 2.03 EPR signal which is a hallmark of dinitrosyl iron complexes, DNIC's. The Fe(NO)(2) unit can be removed from the chelate by excess PhS-, producing (PhS)(2)Fe(NO)(2)(-). Transfer of NO from Fe(H(+)bme-daco)(NO)(2) (v(NO) = 1740, 1696 cm(-1)) to Fell of [(bme-daco)Fe](2) yields the five-coordinate, square-pyramidal N2S2-Fe(NO) (v(NO) = 1649 cm(-1)), where NO is in the apical position. Its isotropic EPR signal at g = 2.05 is consistent with E-F Fe(NO)}(7) formulation. In excess NO, Roussin's red ester-type molecules are formed as dinuclear or tetranuclear species, (mu-SRS)[Fe-2(NO)(4)]}(n) (n =1, 2). These well-characterized molecules furnish reference points for positions and patterns in v(NO) vibrational spectroscopy expected to be useful for in vivo studies of NO degradation of iron-sulfur clusters in ferredoxins.
• Synthesis and Molecular Structures of Mononitrosyl (N₂S₂)M(NO) Complexes (M = Fe, Co)
  作者：Chao-Yi Chiang、Jonghyuk Lee、Christopher Dalrymple、Michael C. Sarahan、Joseph H. Reibenspies、Marcetta Y. Darensbourg

  DOI：10.1021/ic051027s

  日期：2005.11.1

  A series of tetragonally distorted square pyramids of formula N2S2M(NO) (M = Fe, Co) is prepared and characterized by v(NO) IR and EPR spectroscopies, magnetism and electrochemical properties, as well as solid-state crystal structure determinations. While the v(NO) IR frequencies and the ZM-N-O angles indicate differences in the electronic environment of NO consistent with the Enemark-Feltham notation of Fe(NO)}(7) and Co(No)}(8), the reduction potentials, assigned to Fe(NO)(7) + e(-) double left right arrow Fe(NO)}(8) and Co(NO)}(8) + e(-) double left right arrow Co(NO)}(9) respectively, are very similar, and in cases identical, for most members of the series. Coupled with the potential for the M(NO) units to breathe out of and into the N2S2 core plane are unique S-M-N-O torsional arrangements and concomitant pi-bonding interactions which may account for the unusual coherence of reduction potentials within the series.