N,N'-bis(2-methyl-2-mercaptopropyl)-1,5-diazacyclooctane | 152241-93-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N,N'-bis(2-methyl-2-mercaptopropyl)-1,5-diazacyclooctane
• 英文别名: bis(N,N'-2-mercapto-2-methylpropyl)-1,5-diazacyclooctane；1,5 bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctane；1,5-bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctane；H2bme*daco；2-Methyl-1-[5-(2-methyl-2-sulfanylpropyl)-1,5-diazocan-1-yl]propane-2-thiol
• CAS: 152241-93-5
• 化学式: C₁₄H₃₀N₂S₂
• 分子量: 290.538
• InChiKey: UUAYHWGAAHSSHG-UHFFFAOYSA-N

物化性质

• 沸点：
  379.0±42.0 °C(predicted)
• 密度：
  0.990±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  18
• 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：

  N,N'-bis(2-methyl-2-mercaptopropyl)-1,5-diazacyclooctane 以 甲醇 、 甲苯 、 乙腈 为溶剂， 生成 [1-(2-sulfino-2-methylpropyl)-5-(2-sulfino-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II)
  参考文献：
  名称：

  Study of Sulfinate and Sulfenate Complexes Derived from the Oxygenation of Thiolate Sulfur in [1,5-Bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II)

  摘要：

  A series of nickel(II) complexes containing sulfinate and sulfenate S-donor sites has been prepared from systematic oxygenations of the dithiolate complex [1,5-bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) ((bme*-daco)Ni, 1*) and the whole series characterized by mass spectrometry: and X-ray crystallography. The dithiolate complex reacts in organic solvents with molecular oxygen to produce sulfinate (NiS(O)(2)R) complexes, while reactions with hydrogen peroxide have, in addition,permitted the isolation of sulfenate (NiS(O)R) products. The X-ray crystal structures of the complexes [1-(2-mercapto-2-methylpropyl)-5-(2-sulfino-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) (2*), [1,5-bis(2-sulfino-2-methylpropyl)-1,5-diazacyclootanato-(2-)]nickel(II)) (3*), [1,5-bis(2-sulfeno-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) (5*), and [1-(2-sulfeno-2-methylpropyl)-5-(2-sulfino-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) (6*) were determined and metric data compared with previously characterized 1* and 4*, [1-(2-mercapto-2-methylpropyl)-5-(2-sulfeno-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II). Analysis of the Ni-S-(av) bond distances for homoleptic complexes reveals that the bond distances are in the order Ni-S(O)R (2.167(5)) > Ni-SR (2.159(3)) > Ni-S(O)(2)R (2.127(3)). The average nickel sulfinate S-O distance at 1.459 Angstrom is ca. 0.1 Angstrom shorter than the average nickel sulfenate S-O distance at 1.545 Angstrom. These bond dimensions correlated well with spectroscopic and reactivity data. Electrochemical studies find the Ni-II/I reversible couple to be stabilized by ca. 100 mV with conversion of thiolate-S to sulfenate-S donor, while conversion of a sulfenate to a sulfinate stabilized the Ni-I state by an additional 200 mV. Mass spectrometry delineated O-atom loss pathways to dominate initial fragmentation patterns from the parent ions in the protic matrix thioglycerol; however, SO2 extrusion also occurs and is prominent in a nitrobenzyl alcohol (NBA) matrix. The sulfenate complexes are unexpectedly stable and do not undergo either inter- or intramolecular disproportionation reactions to thiolate and sulfinate, nor do they transfer oxygen to triphenyl- or tributylphosphine. Sulfur dioxide removed oxygen from the sulfenates, yielding thiolates and SO3, whereas no reaction occurred with the sulfinate complexes. Complexes that represent partial oxidation of the sulfurs further reacted with hydrogen peroxide to produce higher oxygenates and also reacted with electrophiles such as alkylhalides to produce S-bound sulfoxide ligands.

  DOI：

  10.1021/ja00108a013
• 作为产物：
  描述：

  1,5-二氮杂环辛烷 、 2-甲基-2-丙烯-1-硫醇 以 苯 为溶剂， 反应 48.0h， 以40.8%的产率得到N,N'-bis(2-methyl-2-mercaptopropyl)-1,5-diazacyclooctane
  参考文献：
  名称：

  Study of Sulfinate and Sulfenate Complexes Derived from the Oxygenation of Thiolate Sulfur in [1,5-Bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II)

  摘要：

  A series of nickel(II) complexes containing sulfinate and sulfenate S-donor sites has been prepared from systematic oxygenations of the dithiolate complex [1,5-bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) ((bme*-daco)Ni, 1*) and the whole series characterized by mass spectrometry: and X-ray crystallography. The dithiolate complex reacts in organic solvents with molecular oxygen to produce sulfinate (NiS(O)(2)R) complexes, while reactions with hydrogen peroxide have, in addition,permitted the isolation of sulfenate (NiS(O)R) products. The X-ray crystal structures of the complexes [1-(2-mercapto-2-methylpropyl)-5-(2-sulfino-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) (2*), [1,5-bis(2-sulfino-2-methylpropyl)-1,5-diazacyclootanato-(2-)]nickel(II)) (3*), [1,5-bis(2-sulfeno-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) (5*), and [1-(2-sulfeno-2-methylpropyl)-5-(2-sulfino-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) (6*) were determined and metric data compared with previously characterized 1* and 4*, [1-(2-mercapto-2-methylpropyl)-5-(2-sulfeno-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II). Analysis of the Ni-S-(av) bond distances for homoleptic complexes reveals that the bond distances are in the order Ni-S(O)R (2.167(5)) > Ni-SR (2.159(3)) > Ni-S(O)(2)R (2.127(3)). The average nickel sulfinate S-O distance at 1.459 Angstrom is ca. 0.1 Angstrom shorter than the average nickel sulfenate S-O distance at 1.545 Angstrom. These bond dimensions correlated well with spectroscopic and reactivity data. Electrochemical studies find the Ni-II/I reversible couple to be stabilized by ca. 100 mV with conversion of thiolate-S to sulfenate-S donor, while conversion of a sulfenate to a sulfinate stabilized the Ni-I state by an additional 200 mV. Mass spectrometry delineated O-atom loss pathways to dominate initial fragmentation patterns from the parent ions in the protic matrix thioglycerol; however, SO2 extrusion also occurs and is prominent in a nitrobenzyl alcohol (NBA) matrix. The sulfenate complexes are unexpectedly stable and do not undergo either inter- or intramolecular disproportionation reactions to thiolate and sulfinate, nor do they transfer oxygen to triphenyl- or tributylphosphine. Sulfur dioxide removed oxygen from the sulfenates, yielding thiolates and SO3, whereas no reaction occurred with the sulfinate complexes. Complexes that represent partial oxidation of the sulfurs further reacted with hydrogen peroxide to produce higher oxygenates and also reacted with electrophiles such as alkylhalides to produce S-bound sulfoxide ligands.

  DOI：

  10.1021/ja00108a013

文献信息

• 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
• Adamantane-like Cluster Complexes of Mixed-Valent Copper−Copper and Nickel−Copper Thiolates
  作者：Matthew L. Miller、Said A. Ibrahim、Melissa L. Golden、Marcetta Y. Darensbourg

  DOI：10.1021/ic0262684

  日期：2003.5.1

  utilizing all lone pairs on sulfurs. Further characterization by electrochemical and electronic spectral measurements suggests greater electron delocalization in the all-copper complex as compared to the NiCu heterometallic complex. Mass spectral data imply that the mixed-metal Ni(II)(2)Cu(I)(4)S(4) is more stable toward CuCl loss than Cu(II)(2)Cu(I)(4)S(4), a result that is corroborated by extraction

  顺式二硫代磺酸盐N（2）S（2）配体双（N，N'-2-巯基-2-甲基丙基）-1,5-重氮环辛烷的方形（II）和镍（II）衍生物，（ bme * daco）M，成核四个Cu（I）Cl部分，形成M（II）（2）Cu（I）（4）S（4）簇，簇中有不寻常的三联硫醇盐mu（3）-SR。金刚烷的拓扑形式。通过X射线晶体学测定，（bme * daco）M（M = Cu或Ni）金属硫醇盐可作为双齿配体，利用硫上的所有孤对桥接四个Cu（I）离子。通过电化学和电子光谱测量的进一步表征表明，与NiCu杂金属配合物相比，全铜配合物中有更大的电子离域。质谱数据表明，与Cu（II）（2）Cu（I）（4）S（ 4），
• 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.
• Study of Sulfinate and Sulfenate Complexes Derived from the Oxygenation of Thiolate Sulfur in [1,5-Bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II)
  作者：Rizalia M. Buonomo、Ivan Font、Michael J. Maguire、Joseph H. Reibenspies、Thawatchai Tuntulani、Marcetta Y. Darensbourg

  DOI：10.1021/ja00108a013

  日期：1995.1

  A series of nickel(II) complexes containing sulfinate and sulfenate S-donor sites has been prepared from systematic oxygenations of the dithiolate complex [1,5-bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) ((bme*-daco)Ni, 1*) and the whole series characterized by mass spectrometry: and X-ray crystallography. The dithiolate complex reacts in organic solvents with molecular oxygen to produce sulfinate (NiS(O)(2)R) complexes, while reactions with hydrogen peroxide have, in addition,permitted the isolation of sulfenate (NiS(O)R) products. The X-ray crystal structures of the complexes [1-(2-mercapto-2-methylpropyl)-5-(2-sulfino-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) (2*), [1,5-bis(2-sulfino-2-methylpropyl)-1,5-diazacyclootanato-(2-)]nickel(II)) (3*), [1,5-bis(2-sulfeno-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) (5*), and [1-(2-sulfeno-2-methylpropyl)-5-(2-sulfino-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II) (6*) were determined and metric data compared with previously characterized 1* and 4*, [1-(2-mercapto-2-methylpropyl)-5-(2-sulfeno-2-methylpropyl)-1,5-diazacyclooctanato(2-)]nickel(II). Analysis of the Ni-S-(av) bond distances for homoleptic complexes reveals that the bond distances are in the order Ni-S(O)R (2.167(5)) > Ni-SR (2.159(3)) > Ni-S(O)(2)R (2.127(3)). The average nickel sulfinate S-O distance at 1.459 Angstrom is ca. 0.1 Angstrom shorter than the average nickel sulfenate S-O distance at 1.545 Angstrom. These bond dimensions correlated well with spectroscopic and reactivity data. Electrochemical studies find the Ni-II/I reversible couple to be stabilized by ca. 100 mV with conversion of thiolate-S to sulfenate-S donor, while conversion of a sulfenate to a sulfinate stabilized the Ni-I state by an additional 200 mV. Mass spectrometry delineated O-atom loss pathways to dominate initial fragmentation patterns from the parent ions in the protic matrix thioglycerol; however, SO2 extrusion also occurs and is prominent in a nitrobenzyl alcohol (NBA) matrix. The sulfenate complexes are unexpectedly stable and do not undergo either inter- or intramolecular disproportionation reactions to thiolate and sulfinate, nor do they transfer oxygen to triphenyl- or tributylphosphine. Sulfur dioxide removed oxygen from the sulfenates, yielding thiolates and SO3, whereas no reaction occurred with the sulfinate complexes. Complexes that represent partial oxidation of the sulfurs further reacted with hydrogen peroxide to produce higher oxygenates and also reacted with electrophiles such as alkylhalides to produce S-bound sulfoxide ligands.