[1,5-bis(2-mercaptoethyl)-1,5-diazacyclooctane]nickel(II) | 129964-91-6

• 分子结构分类: 有机化合物
• 英文名称: [1,5-bis(2-mercaptoethyl)-1,5-diazacyclooctane]nickel(II)
• 英文别名: [1,5-bis(mercaptoethyl)-1,5-diazacyclooctanoato]nickel(II)；bis(mercaptoethane)diazacyclooctane nickel(II)；Ni(1,5-bis(mercaptoethyl)-1,5-diazacyclooctane(2-))；[N,N'-bis(2-mercaptoethyl)-1,5-diazacyclooctane]nickel(II)；(N,N'-bis(2-mercaptoethyl)-1,5-diazacyclooctanato)nickel(II)；nickel(II) N,N'-bis-2-mercaptoethyl-N,N'-diazocyclooctane；(N,N'-bis-2-mercaptoethyl-1,5-diazacycloctane)nickel(II)；N,N'-bis(mercaptoethyl)-1,5-diazacylooctanenickel(II)；[Ni(N,N'-bis(2-mercaptoethyl)-1,5-diazacyclooctano)]；[(bmedaco)Ni]；nickel(2+);2-[5-(2-sulfidoethyl)-1,5-diazocan-1-yl]ethanethiolate
• CAS: 129964-91-6
• 化学式: C₁₀H₂₀N₂NiS₂
• 分子量: 291.104
• InChiKey: FDIOPSSHONXBON-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-mercaptoethyl)-1,5-diazacyclooctane]nickel(II) 在 SO₂ 作用下， 以 甲醇 为溶剂， 以60%的产率得到(N,N'-bis(mercaptoethyl)-1,5-diazacyclooctane)nickel(II) * sulfur dioxide
  参考文献：
  名称：

  Darensbourg, Marcetta Y.; Tuntulani, Thawatchai; Reibenspies, Joseph H., Inorganic Chemistry, 1994, vol. 33, # 3, p. 611 - 613

  摘要：

  DOI：
• 作为产物：
  描述：

  (N,N'-bis(mercaptoethyl)-1,5-diazacyclooctane)nickel(II) * sulfur dioxide 以 乙腈 为溶剂， 生成 [1,5-bis(2-mercaptoethyl)-1,5-diazacyclooctane]nickel(II)
  参考文献：
  名称：

  Darensbourg, Marcetta Y.; Tuntulani, Thawatchai; Reibenspies, Joseph H., Inorganic Chemistry, 1994, vol. 33, # 3, p. 611 - 613

  摘要：

  DOI：
• 作为试剂：
  描述：

  二氧化硫 、 氧气 在 [1,5-bis(2-mercaptoethyl)-1,5-diazacyclooctane]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。
• CO and Ethylene Migratory Insertion Reactions and Copolymerization Involving Palladium Complexes of a NiN₂S₂ Metallodithiolate Ligand
  作者：Marilyn V. Rampersad、Erik Zuidema、Jan Meine Ernsting、Piet W. N. M. van Leeuwen、Marcetta Y. Darensbourg

  DOI：10.1021/om0605783

  日期：2007.2.1

  analogues. It was further shown that displacement of the terminally bound CO by ethylene in the acetylated derivative [(Ni-1)Pd(C(O)CH3)(CO)]+ was slow, attributable to the high binding affinity of CO toward Pd2+ in the presence of the electron-rich nickel dithiolate ligand. Bulk copolymerization studies of CO/ethylene in the presence of the cationic catalyst precursor [(Ni-1)Pd(CH3)(OEt2)][BAr‘4]

  中性（（Ni基1）的Pd（CH 3）（CL））和阳离子（[（Ni基1）的Pd（CH 3）（OET 2）] [BAR” 4 ]）含有强供电子metallodithiolate配体络合物制备了Ni-1（[（N，N'-双（2-巯基乙基）-N，N'-二氮杂环辛烷]镍（II）。通过红外和高压研究了这些Pd-烷基配合物的羰基化反应NMR光谱。碳13 NMR光谱研究表明CO插入形成衍生物（Ni-1）Pd（C（O）CH 3）（Cl）和[（Ni-1）Pd（C（O）CH 3）（CO）] +在-80°C的CD 2 Cl 2中具有不可估量的快性，而基于Pd金属的二膦和二亚胺类似物的速率较慢。进一步表明，在乙酰化衍生物[（Ni-1）Pd（C（O）CH 3）（CO）] +中，乙烯对末端键合的CO的置换很慢，这归因于CO对Pd的高结合亲和力在富电子的二硫代镍配体存在下为2+。在阳离子催化剂前体[（存在CO /乙烯的本体共聚研究的Ni-1
• A matrix of heterobimetallic complexes for interrogation of hydrogen evolution reaction electrocatalysts
  作者：Pokhraj Ghosh、Shengda Ding、Rachel B. Chupik、Manuel Quiroz、Chung-Hung Hsieh、Nattami Bhuvanesh、Michael B. Hall、Marcetta Y. Darensbourg

  DOI：10.1039/c7sc03378h

  日期：——

  address key questions in a structure-function analysis of bioinspired electrocatalysts for the HER. Combinations of NiN2S2 or [(NO)Fe]N2S2 as donors to (η5-C5H5)Fe(CO)+ or [Fe(NO)2]+/0 generate a series of four bimetallics, gradually “softened” by increasing nitrosylation, from 0 to 3, by the non-innocent NO ligands. The nitrosylated NiFe complexes are isolated and structurally characterized in two redox

  实验和计算研究解决了 HER 仿生电催化剂结构功能分析中的关键问题。NiN 2 S 2或 [(NO)Fe]N 2 S 2作为 (η 5 -C 5 H 5 )Fe(CO) +或 [Fe(NO) 2 ] +/0供体的组合生成一系列四个双金属化合物，通过非无辜的 NO 配体增加亚硝基化（从 0 到 3）逐渐“软化”。亚硝基化 NiFe 配合物被分离出来，并在两个氧化还原水平上进行结构表征，证明了电催化所需的特征。对实验结构和连接电化学事件的可能瞬态中间体的计算模型发现，NO 导致电子离域，以及 Fe-S 键解离，产生末端硫醇盐作为侧基，位置良好，有利于质子的吸收和转移。“较硬”双金属排列的内部 SH + ••• − H-Fe 单元具有更集中的电子密度，通过质子/氢化物耦合形成氢气，而较软的单元通过两个 Fe- 的还原消除来转化 H − •••H − H 源自高度离域、双还原的 [Fe 2 (NO)
• 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)