(OC)3Fe((CH2)3S2)Ni(Ph2P(CH2)2PPh2) | 877034-21-4

• 英文名称: (OC)3Fe((CH2)3S2)Ni(Ph2P(CH2)2PPh2)
• 英文别名: (OC)₃Fe((CH₂)₃S₂)Ni(Ph₂P(CH₂)₂PPh₂)；(OC)₃Fe(pdt)Ni(1,2-bis-(diphenylphosphino)ethane)；(dppe)Ni(μ-pdt)Fe(CO)₃；[(dppe)Ni(pdt)Fe(CO)₃]；(OC)₃Fe(pdt)Ni(dppe)；[NiFe(1,3-propanedithiolate)(1,2-bis(diphenylphosphino)ethane)(CO)3]；NiFe(1,3-propanedithiolate)(1,2-bis(diphenylphosphino)ethane)(CO)3
• CAS: 877034-21-4；877034-22-5
• 化学式: C₃₂H₃₀FeNiO₃P₂S₂
• 分子量: 703.205
• InChiKey: ACGVTCARCGJZPV-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：
  None
• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  (OC)3Fe((CH2)3S2)Ni(Ph2P(CH2)2PPh2) 在 pentane 作用下， 以 二氯甲烷 为溶剂， 生成 [(dppe)Ni(propaneditiolate)Fe(CO)2(PMe2Ph)2](BF4)2
  参考文献：
  名称：

  [NiFe]-氢化酶活性位点的混合价镍-铁二硫醇模型

  摘要：

  描述了一系列混合价镍铁二硫醇盐。(diphosphine)Ni(dithiolate)Fe(CO) 3配合物1、2和3与二茂铁盐的氧化得到相应的三羰基阳离子 [(dppe)Ni(pdt)Fe(CO) 3 ] + ([ 1 ] + ) , [(dppe)Ni(edt)Fe(CO) 3 ] + ([ 2 ] + ) 和 [(dcpe)Ni(pdt)Fe(CO) 3 ] + ([ 3 ] + )，其中 dppe = Ph 2 PCH 2 CH 2 PPh2，dcpe = Cy 2 PCH 2 CH 2 PCy 2，（Cy = 环己基），pdtH 2 = HSCH 2 CH 2 CH 2 SH，和edtH 2 = HSCH 2 CH 2 SH。阳离子 [ 2 ] +证明是不稳定的，但丙二硫醇盐是稳定的。IR 和 EPR 光谱测量表明这些物质作为C s对称物质存在。[ 3 ]BF 4 的晶体学表征表明Ni是方形平面。[

  DOI：

  10.1021/ic202329y
• 作为产物：
  描述：

  在 双(环戊二烯)钴 作用下， 以 二氯甲烷 为溶剂， 以13.9 mg的产率得到(OC)3Fe((CH2)3S2)Ni(Ph2P(CH2)2PPh2)
  参考文献：
  名称：

  [NiFe] 氢化酶的 (57) Fe 标记模型的合成和振动光谱：首次直接观察镍-铁相互作用。

  摘要：

  一种制备羰基铁的新途径使 (57)Fe 标记的 [NiFe] 氢化酶模拟物 (OC)3(57)Fe(pdt)Ni(dppe) 的合成成为可能。其核共振振动光谱研究揭示了 Ni-(57)Fe 振动，正如计算所证实的那样。[(OC)3(57)Fe(pdt)Ni(dppe)](+) 不存在模式，它缺乏 Ni-(57)Fe 键合，强调了分析在识别金属-金属相互作用方面的效用。

  DOI：

  10.1039/c4cc04572f

文献信息

• Synthetic Models for Nickel–Iron Hydrogenase Featuring Redox-Active Ligands
  作者：David Schilter、Danielle L. Gray、Amy L. Fuller、Thomas B. Rauchfuss

  DOI：10.1071/ch16614

  日期：——

  NiIIFeIFeII complexes [(diphosphine)Ni(dithiolate)Fe(CO)2(ferrocenylphosphine)]+ (diphosphine = Ph2P(CH2)2PPh2 or Cy2P(CH2)2PCy2; dithiolate = –S(CH2)3S–; ferrocenylphosphine = diphenylphosphinoferrocene, diphenylphosphinomethyl(nonamethylferrocene) or 1,1′-bis(diphenylphosphino)ferrocene). The hydride species is a catalyst for hydrogen evolution, while the latter hydride-free complexes can exist in

  镍铁氢酶有效且可逆地相互转化质子，电子和二氢。这些氧化还原蛋白具有铁硫簇，可将电子往返于其活性位。此处报道的是镍铁氢化酶的合成模型，其特征在于具有氧化还原活性的助剂，可模拟铁硫辅助因子。制备的复合物为Ni II（μ-H）的Fe II的Fe II物种式[（二膦）镍（二硫醇）（μ-H）的Fe（CO）2（二茂铁）] +或Ni II的Fe我铁II络合物[ （二膦基）Ni（二硫代硫酸盐）Fe（CO）2（二茂铁基膦）] +（二膦基= Ph2 P（CH 2）2 PPh 2或Cy 2 P（CH 2）2 PCy 2；二硫代盐=  – S（CH 2）3 S –; 二茂铁基膦＝二苯基膦基二茂铁，二苯基膦基甲基（九甲基二茂铁）或1，1′-双（二苯基膦基）二茂铁。氢化物是氢释放的催化剂，而后者的无氢化物络合物可以四个氧化还原态存在-铁二茂铁基团的引入使这一特征成为可能。1,1'-双（二苯基膦基）二茂铁的混合价络合物
• Active-Site Models for the Nickel–Iron Hydrogenases: Effects of Ligands on Reactivity and Catalytic Properties
  作者：Maria E. Carroll、Bryan E. Barton、Danielle L. Gray、Amanda E. Mack、Thomas B. Rauchfuss

  DOI：10.1021/ic2012759

  日期：2011.10.3

  nickel as well as the dithiolate bridge, 1,3-propanedithiolate (pdt) vs 1,2-ethanedithiolate (edt). A new synthetic route to these Ni–Fe dithiolates is described, involving reaction of Ni(SR)2(diphosphine) with FeI2(CO)4 followed by in situ reduction with cobaltocene. Evidence is presented that this route proceeds via a metastable μ-iodo derivative. Attempted isolation of such species led to the crystallization

  描述了[HNiFe(SR) 2 (二膦)(CO) 3 ] +类型的新衍生物，其特征在于Ni(二膦)基团通过两个桥接硫醇盐配体连接到Fe(CO) 3基团。先前的工作描述了 [HNiFe(pdt)(dppe)(CO) 3 ] + ([ 1 H] + ) 及其作为还原质子催化剂的活性 ( J. Am. Chem. Soc. 2010 , 132, 14877)。本文中描述的工作重点是对连接在镍上的二膦以及二硫醇桥、1,3-丙二硫醇 (pdt) 与 1,2-乙二硫醇 (edt) 的 NiFe 模型复合物性质的影响。描述了这些 Ni-Fe 二硫醇盐的新合成路线，包括 Ni(SR) 2（二膦）与 FeI 2 (CO) 4 的反应，然后用二茂钴原位还原。有证据表明该路线通过亚稳态 μ-碘衍生物进行。尝试分离此类物质导致 NiFe(Me 2 pdt)(dppe)I 2结晶，其特征是四面体 Fe(II) 和方形平面
• Nickel–iron dithiolates related to the deactivated [NiFe]-hydrogenases
  作者：David Schilter、Thomas B. Rauchfuss

  DOI：10.1039/c2dt31895d

  日期：——

  preparations of synthetic models for the deactivated Ni(II)Fe(II) states of the [NiFe]-hydrogenases. Iodination of the S = ½ species [(dppe)Ni(pdt)Fe(CO)3]+ afforded the diamagnetic iodo complex [(dppe)Ni(pdt)IFe(CO)3]+. Crystallographic analysis of this species confirmed the presence of square-pyramidal Ni linked to an octahedral Fe centre. The Ni⋯Fe separation of 3.018 Å indicated the absence of metal–metal

  本文描述了[NiFe]-氢化酶的失活Ni( II )Fe( II )态的合成模型的制备。所述的碘化小号=½物种[（DPPE）的Ni（PDT）的Fe（CO）3 ] +，得到反磁性碘配合物[（DPPE）的Ni（PDT）IFE（CO）3 ] +。该物种的晶体学分析证实了与八面体 Fe 中心相连的方形锥体 Ni 的存在。3.018 Å 的 Ni⋯Fe 分离表明没有金属-金属键合。该配合物可被还原为 (DPPE)Ni(pdt)Fe(CO) 3 ，并在碘化物存在下脱羰得到 (DPPE)Ni(pdt)FeI 2. [(diphosphine)Ni(dithiolate)XFe(CO) 2 L] + (X = Cl, Br, I) 类型的衍生物是通过卤化混合价前体 [(diphosphine)Ni(dithiolate)Fe(CO) 2 L] +（二膦 = DPPE、dcpe；L = 叔膦或 CO）。含 Fe(CO)
• Hydride-Containing Models for the Active Site of the Nickel−Iron Hydrogenases
  作者：Bryan E. Barton、Thomas B. Rauchfuss

  DOI：10.1021/ja105312p

  日期：2010.10.27

  The [NiFe]-hydrogenase model complex NiFe(pdt)(dppe)(CO)(3) (1) (pdt = 1,3-propanedithiolate) has been efficiently synthesized and found to be robust. This neutral complex sustains protonation to give the first nickel-iron hydride [1H]BF4. One CO ligand in [1H]BF4 is readily substituted by organophosphorus ligands to afford the substituted derivatives [HNiFe(pdt)(dppe)(PR3)(CO)(2)]BF4, where PR3 = P(OPh)(3) ([2H]BF4); PPh3 ([3H]BF4); PPh2Py ([4H]BF4, where Py = 2-pyridyl). Variable temperature NMR measurements show that the neutral and protonated derivatives are dynamic on the NMR time scale, which partially symmetrizes the phosphine complex. The proposed stereodynamics involve twisting of the Ni(dppe) center, not rotation at the Fe(CO)(2)(PR3) center. In MeCN solution, 3, which can be prepared by deprotonation of [3H]BF4 with NaOMe, is about 10(4) stronger base than is 1. X-ray crystallographic analysis of [3H]BF4 revealed a highly unsymmetrical bridging hydride, the Fe-H bond being 0.40 angstrom shorter than the Ni-H distance. Complexes [2H]BF4, [3H]BF4, and [4H]BF4 undergo reductions near -1.46 V vs Fc(0/+). For [2H]BF4, this reduction process is reversible, and we assign it as a one-electron process. In the presence of trifluoroacetic acid, proton reduction catalysis coincides with this reductive event. The dependence of i(c)/i(p) on the concentration of the acid indicates that H-2 evolution entails protonation of a reduced hydride. For [2H](+), [3H](+), and [4H](+), the acid-independent rate constants are 50-75 s(-1). For [2H](+) and [3H](+), the overpotentials for H-2 evolution are estimated to be 430 mV, whereas the overpotential for the N-protonated pyridinium complex [4H(2)](2+) is estimated to be 260 mV. The mechanism of H-2 evolution is proposed to follow an ECEC sequence, where E and C correspond to one-electron reductions and protonations, respectively. On the basis of their values for its pK(a) and redox potentials, the room temperature values of Delta G(H center dot) and Delta G(H center dot) are estimated as respectively as 57 and 79 kcal/mol for [1H](+).
• Barton, Bryan E.; Whaley, C. Matthew; Rauchfuss, Thomas B., Journal of the American Chemical Society, 2009, vol. 131, p. 6942 - 6943
  作者：Barton, Bryan E.、Whaley, C. Matthew、Rauchfuss, Thomas B.、Gray, Danielle L.

  DOI：——

  日期：——