[1,5-bis(2-mercapto-2-methylpropane)-1,5-diazacyclooctanato]nickel(II) | 152385-47-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫代缩醛
• 英文名称: [1,5-bis(2-mercapto-2-methylpropane)-1,5-diazacyclooctanato]nickel(II)
• 英文别名: 1,5-bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctanato(2-)nickel(II)；(N,N'-bis(2-mercapto-2-methylpropyl)-1,5-dizacyclooctanato)nickel(II)；N,N'-bis(2-mercapto-2-methylpropane)-1,5-diazacyclooctanenickel(II)；(N,N'-bis-(2-mercapto-2-methylpropyl)-1,5-diazacyclooctane)nickel(II)；[N,N'-bis(2,2-dimethyl-2-mercaptoethyl)-1,5-diazacyclooctanoato]nickel(II)；2-methyl-1-[5-(2-methyl-2-sulfidopropyl)-1,5-diazocan-1-yl]propane-2-thiolate;nickel(2+)
• CAS: 152385-47-2
• 化学式: C₁₄H₂₈N₂NiS₂
• 分子量: 347.212
• InChiKey: DBXIFEQHQNUIKQ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [1,5-bis(2-mercapto-2-methylpropane)-1,5-diazacyclooctanato]nickel(II) 在 CH₃I 作用下， 以 乙腈 为溶剂， 以86%的产率得到[1-(2-mercapto-2-methylpropyl)-5-(2-thia-3,3-dimethylbutyl)-1,5-diazacyclooctanato]nickel(II) iodide complex
  参考文献：
  名称：

  Correlation of electrochemistry, nucleophilicity and density functional calculations of the cis-dithiolate (bme*-daco)Ni

  摘要：

  Upon the sequential stoichiometric addition of methyl iodide to acetonitrile solutions of the square planar nickel (II) complex of N,N'-bis(2-mercapto-2-methylpropyl)-1,5-diazacyclooctane, (bme*-daco)Ni, mono- and bis-methylated thioether compounds were isolated. Both are crystallographically and electrochemically characterized and compared to analogues of N,N'-bis(2-mercaptoethyl)-1,5-diazacyclooctane, (bme-daco)Ni. Density functional theory calculations carried out at the B3LYP level using the LANL2DZ basis set with modified exponents compared HOMO/LUMO energies for the dithiolates, the mono-S-methylated and bis-S-methylated complexes. The presence of the methyl groups on the alpha-carbon next to the sulfur creates steric encumbrance about the thiolate sulfurs, but there was found no significant differences in the frontier molecular orbitals. The more positive shifts of the Ni(II/I) reduction potentials are reflected by changes in LUMO energies upon S-methylation. (C) 2000 Elsevier Science S.A. All rights reserved.

  DOI：

  10.1016/s0020-1693(99)00575-7
• 作为产物：
  描述：

  N-(2-mercapto-2-(methylpropyl))-N'-(2-sulfenato-2-(methylpropyl))-1,5-diazacyclooctanenickel(II) 以 甲醇 为溶剂， 生成 [1,5-bis(2-mercapto-2-methylpropane)-1,5-diazacyclooctanato]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
• 作为试剂：
  描述：

  二氧化硫 、 氧气 在 [1,5-bis(2-mercapto-2-methylpropane)-1,5-diazacyclooctanato]nickel(II) NaSPh 作用下， 以 甲醇 为溶剂， 生成 硫酸酯
  参考文献：
  名称：

  Structure/Function Relationships in Ligand-Based SO2/O2 Conversion to Sulfate As Promoted by Nickel and Palladium Thiolates

  摘要：

  The dithiolate complex [1,5-bis(mercaptoethyl)-1,5-diazacyclooctane]Pd(II), (bme-daco)Pd-II or Pd-1, whose structure was determined by X-ray crystallography (monoclinic P2(1)/m space group with a = 6.1680(10) Angstrom, b = 15.715(5) Angstrom, c = 6.5930(10) Angstrom, beta = 107.090(10)degrees, Z = 2, R = 0.0291, R(W) = 0.0718), has been added to a group of metal thiolates which form sulfur-site SO2 adducts. Exposure of the Pd-l complex to SO2 in methanol results in the precipitation of yellow/orange crystalline Pd-1 SO2: monoclinic space group, P2(1)/c (No. 14), with a 8.928(2) Angstrom, b = 14.655(4) Angstrom, c = 11.067(2) Angstrom, beta = 97.29(2)degrees, Z = 4, R = 0.0348, R(W) = 0.0944. Analogous thiolate-SO2 adducts based on (bme-daco)Ni-II, Ni-1 . SO2, (Ph(2)PCH(2)CH(2)S)(2)Ni-II, Ni-2 . SO2, and (bme*-daco)Ni-II, Ni-1*. SO2, also precipitate from methanol. To explore the transformation of SO2 to SO42- in these adducts, the following three factors expected to control the sulfate-forming reaction have been examined: (i) the stability of SO2 adducts; (ii) the oxidizability of the metal thiolate or its tendency to generate disulfide products on oxidation; and (iii) the ability of the metal thiolates to react with O-2 and produce sulfur-oxygenated products. The studies indicate that the last factor is the most important influence on SO2 oxygenation. A possible mechanism involves the transient formation of an SO2-stabilized sulfperoxide intermediate, which behaves as a nucleophile and further reacts with SO2 to produce SO42-. The use of the aforementioned metal thiolate complexes as catalysts for SO2 oxygenation in the presence of a sacrificial electron donor has also been explored; simple salts such as NiCl2 and NiSO4 are more efficient than the complexes.

  DOI：

  10.1021/ic00129a013

文献信息

• Models for Terminal Ni(S-Cysteine) Modification in [NiFe]Hydrogenases by Iodoacetamide and Iodoacetate
  作者：Jason J. Smee、Dawn C. Goodman、Joseph H. Reibenspies、Marcetta Y. Darensbourg

  DOI：10.1002/(sici)1099-0682(199903)1999:3<539::aid-ejic539>3.0.co;2-y

  日期：1999.3

  complex [N,N′-bis(2-mercaptoethyl-2-methylpropyl)-1,5-diazacyclooctane]nickel(II) (Ni-1*) reacts with stoichiometric amounts of iodoacetamide to yield S-alkylated, mono- and diacetamide complexes, [(AA)Ni-1*][I] and [(AA)2Ni-1*][I]2. Their molecular structures are established by X-ray crystallography and find the former in pseudo-square planar geometry with no additional coordination of the amide functionality

  顺式二硫醇配合物 [N,N'-双(2-巯基乙基-2-甲基丙基)-1,5-二氮杂环辛烷]镍 (II) (Ni-1*) 与化学计量的碘乙酰胺反应生成 S-烷基化的，单乙酰胺和双乙酰胺配合物，[(AA)Ni-1*][I] 和 [(AA)2Ni-1*][I]2。它们的分子结构是通过 X 射线晶体学建立的，在伪正方形平面几何形状中发现前者没有酰胺官能团的额外配位，而后者是八面体 N2S2O2NiII 复合物。将轴向配位配体指定为酰胺氧原子与固体和溶液状态的红外光谱 ν(C=O) 结果一致。通过紫外/可见光谱、电导测量和电化学研究进一步表征复合物。
• Singlet Oxygen and the Production of Sulfur Oxygenates of Nickel(II) and Palladium(II) Thiolates
  作者：Craig A. Grapperhaus、Michael J. Maguire、Thawatchai Tuntulani、Marcetta Y. Darensbourg

  DOI：10.1021/ic970050d

  日期：1997.4.1

  acetonitrile and sulfoxides favored in methanol. There is also a ligand and metal effect. The proposed mechanistic pathways involving a persulfoxide precursor to single sulfur site O(2) addition (producing metallosulfones) and adjacent sulfur site O(2) addition (producing metallosulfoxides) are consistent with product distribution, comparison to the much studied oxygenation of organic sulfides, and previous

  二硫醇金属[1,5-双（2-巯基乙基）-1,5-二氮杂环辛烷]镍（II）（Ni-1），位阻类似物（Ni-1）和钯类似物Pd-1与之反应（1）Delta O（2）产生各种稳定且可分离的金属氯砜（MS（O（2））R）和金属氯亚砜（MS（O）R）。通过敏化剂Rose Bengal光化学产生单线态氧，并通过1,4-二甲基萘的1,4-内过氧化物分解产生热态单线态氧。O（2）从其基态（3）Sigma激发到激发态（1）Delta时，观察到速率增加和氧合产率增加。反应取决于溶剂和浓度，其中乙腈中通常优选砜，而甲醇中通常优选亚砜。还有配体和金属效应。
• Ruthenium Derivatives of NiS₂N₂ Complexes as Analogues of Bioorganometallic Reaction Centers
  作者：Michael A. Reynolds、Thomas B. Rauchfuss、Scott R. Wilson

  DOI：10.1021/om020724e

  日期：2003.4.1

  3-diaminoethane) gives [Cp*Ru(NiS2N2)]2(OTf)2 ([1]2(OTf)2), which exists as a monomer−dimer equilibrium in MeCN solution. Crystallographic analysis of [1]2(OTf)2 reveals a centrosymmetric dication with the Ru being quasi-octahedral and the NiS2N2 coordination sphere being relatively planar, the metal centers being linked via pairs of μ2-SR and μ3-SR units. Complex [1]22+ oxygenates and sulfidizes with

  结构生物学的最新结果表明，Ni（SR）2 L 2中心附着在结合CO的第二种金属上，尤其是NiFe氢化酶和乙酰​​CoA合酶上，具有催化作用。在旨在开发对CO具有亲和力的双金属衍生物的实验中，我们研究了二氨基二硫代镍盐的Ru（II）衍生物以及这些配合物对CO和其他小分子的反应性。的反应的[Cp *茹（NCMe）3 ]光学传递函数和NIS 2 Ñ 2（S 2 Ñ 2 = N，N-双（2-巯基乙基） - N，N- ' -二甲基-1,3-二氨基乙烷），得到[Cp * Ru（NiS 2 N 2）] 2（OTf）2（[ 1 ] 2（OTf）2），它作为MeCN溶液中的单体-二聚体平衡存在。的[结晶学分析1 ] 2（OTF）2揭示了与钌是准八面体和所述的NiS中心对称的双阳离子2 Ñ 2配位层是相对平坦的，通过对μ的被连接的金属中心2 -SR和μ 3 - SR单位。配合物[ 1 ] 2 2+分别与O 2和S
• Characterization of Steric and Electronic Properties of NiN₂S₂ Complexes as S-Donor Metallodithiolate Ligands
  作者：Marilyn V. Rampersad、Stephen P. Jeffery、Melissa L. Golden、Jonghyuk Lee、Joseph H. Reibenspies、Donald J. Darensbourg、Marcetta Y. Darensbourg

  DOI：10.1021/ja055051g

  日期：2005.12.1

  The physical properties and structures of a series of six complexes of the type (NiN(2)S(2))W(CO)(4) have been used to establish electronic and steric parameters for square planar NiN(2)S(2) complexes as bidentate, S-donor ligands. According to the nu(CO) stretching frequencies and associated computed Cotton-Kraihanzel force constants of the tungsten carbonyl adducts, there is little difference in

  一系列六种 (NiN(2)S(2))W(CO)(4) 配合物的物理性质和结构已被用于建立方形平面 NiN(2)S(2) 的电子和空间参数) 复合物作为双齿 S 供体配体。根据 nu(CO) 拉伸频率和相关计算的 Cotton-Kraihanzel 力常数的钨羰基加合物，该系列中五个中性 NiN(2)S(2) 金属二硫醇配体的供体能力几乎没有差异。双离子 Ni(ema)(2)(-) (ema = N,N'-ethylenebis(2-mercaptoacetamide)) 复合物将更多的电子密度转移到 W(CO)(4) 部分。供体能力排名以及与经典双齿配体的比较如下：Ni(ema)(=) > [NiN(2)S(2)](0)} > bipy大约 phen > Ph(2)PCH( 2)CH(2)PPh(2) > Ph(2)PCH(2)PPh(2)。来自循环伏安法的电化学数据发现 (NiN(2)S(2))W(CO)(4)
• 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），