{Ni-Di(phenylsulfid)-(1.2-Bis-diphenylphosphino-aethan)} | 62637-81-4

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: {Ni-Di(phenylsulfid)-(1.2-Bis-diphenylphosphino-aethan)}
• 英文别名: (1,2-bis(diphenylphosphino)ethane)Ni(thiophenolate)2；(dppe)Ni(SPh)2；Ni(SPh)2(1,2-bis(diphenylphosphino)ethane)；benzenethiolate;2-diphenylphosphanylethyl(diphenyl)phosphane;nickel(2+)
• CAS: 62637-81-4
• 化学式: C₃₈H₃₄NiP₂S₂
• 分子量: 675.457
• InChiKey: MMHAJIAMGLSACN-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  8.43
• 重原子数：
  43
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,6-lutidinium tetraphenylborate 、 {Ni-Di(phenylsulfid)-(1.2-Bis-diphenylphosphino-aethan)} 以 乙腈 为溶剂， 生成 Ni(dppe)(SC6H5)2H(1+)
  参考文献：
  名称：

  Proton Transfer to Nickel−Thiolate Complexes. 1. Protonation of [Ni(SC₆H₄R-4)₂(Ph₂PCH₂CH₂PPh₂)] (R = Me, MeO, H, Cl, or NO₂)

  摘要：

  The kinetics of the equilibrium reaction between [Ni(SC6H4R-4)(2)(dppe)] (R = MeO, Me, H, Cl, or NO2; dppe = Ph2PCH2CH2PPh2) and mixtures of [lutH](+) and lut (lut = 2,6-dimethylpyridine) in MeCN to form [Ni(SHC6H4R-4)(SC6H4R-4)(dppe)](+) have been studied using stopped-flow spectrophotometry. The kinetics for the reactions with R = MeO, Me, H, or Cl are consistent with a single-step equilibrium reaction. Investigation of the temperature dependence of the reactions shows that DeltaG(double dagger) = 13.6 +/- 0.3 kcal mol(-1) for all the derivatives but the values of DeltaH(double dagger) and DeltaS(double dagger) vary with R (R = MeO, DeltaH(double dagger) = 8.5 kcal mol(-1), DeltaS(double dagger) = -16 cal K-1 mol(-1); R = Me, DeltaH(double dagger) = 10.8 kcal mol(-1), DeltaS(double dagger) = -9.5 cal K-1 mol(-1); R = Cl, DeltaH(double dagger) = 23.7 kcal mol(-1), DeltaS(double dagger) = +33 cal K-1 mol(-1)). With [Ni(SC6H4NO2-4)(2)(dppe)] a more complicated rate law is observed consistent with a mechanism in which initial hydrogen-bonding of [lutH](+) to the complex precedes intramolecular proton transfer, It seems likely that all the derivatives operate by this mechanism, but only with R = NO2 (the most electron-withdrawing substituent) does the intramolecular proton transfer step become sufficiently slow to result in the change in kinetics. Studies with [lutD]+ show that the rates of proton transfer to [Ni(SC6H4R-4)(2)(dppe)] (R = Me or Cl) are associated with negligible kinetic isotope effect. The possible reasons for this are discussed. The rates of proton transfer to [Ni(SC6H4R-4)(2)(dppe)] vary with the 4-R-substituent, and the Hammett plot is markedly nonlinear. This unusual behavior is attributable to the electronic influence of R which affects the electron density at the sulfur.

  DOI：

  10.1021/ic030322e
• 作为产物：
  描述：

  dibromo[1,2-bis(diphenylphosphino)ethane]nickel(II) 在 NaI 作用下， 以 乙醇 、 水 为溶剂， 生成 {Ni-Di(phenylsulfid)-(1.2-Bis-diphenylphosphino-aethan)}
  参考文献：
  名称：

  Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Ni: MVol.C2, 8.20, page 1073 - 1085

  摘要：

  DOI：

文献信息

• Synthetic analogs for evaluating the influence of N–H⋯S hydrogen bonds on the formation of thioester in acetyl coenzyme a synthase
  作者：Piyal W. G. Ariyananda、Matthew T. Kieber-Emmons、Glenn P. A. Yap、Charles G. Riordan

  DOI：10.1039/b901192g

  日期：——

  (dRpe)Ni(CO)(2) and MeC(O)SAr via the intermediacy of the acylnickel adducts, (dRpe)Ni(C(O)Me)(SAr), detected at low temperature by (31)P NMR spectroscopy. Consistent with experimental observations, density functional theory results reveal that the intramolecular hydrogen bond in 9 stabilizes the acylnickel adduct compared with its non-hydrogen-bonded adduct, 10. Oxidative addition of MeC(O)SC(6)F(5) to (dRpe)Ni(COD)

  一系列方形平面甲基镍（II）配合物，（dppe）Ni（Me）（SAr）（dppe = 1,2-双（二苯基膦）乙烷）；2. Ar = 苯基；3. Ar = 五氟苯基；4. Ar = 邻新戊酰氨基苯基；5. Ar = 对新戊酰氨基苯基；(depe)Ni(Me)(SAr)，(depe = 1,2-双(二乙基膦)乙烷)；7. Ar = 苯基；8. Ar = 五氟苯基；9. Ar = 邻新戊酰氨基苯基；10. Ar = p-新戊酰氨基苯基)，通过 (dppe)NiMe(2) (1) 和 (depe)NiMe(2) (6) 与相应的硫醇或二硫化物反应合成。这些配合物通过各种光谱方法进行表征，包括 (31) P NMR、(1) H NMR、(13) C NMR 和红外光谱，并且在大多数情况下通过 X 射线衍射分析。固态和溶液测量确定 4 和 9 包含分子内 NH...S 键。配合物 2-4 的羰基化，7-10
• Some mercaptides and mercaptide complexes of nickel and palladium
  作者：R.G. Hayter、F.S. Humiec

  DOI：10.1016/0022-1902(64)80326-2

  日期：1964.5

  Two methods for the preparation of nickel mercaptide complexes of the type [Ni(SC6H5)2L2] (L = (C2H5)3P, C6H5(CH3)2P and L2 = (C6H5)2PCH2CH2P(C6H5)2) are described. The complexes are square planar and dissociate readily in solution. Analogous palladium complexes are reported and the structures of the palladium mercaptides, [Pd(SR)2]n, discussed.

  制备[Ni（SC 6 H 5）2 L 2 ]类型的硫醇镍配合物的两种方法（L =（C 2 H 5）3 P，C 6 H 5（CH 3）2 P和L 2 = （C 6 H 5）2 PCH 2 CH 2 P（C 6 H 5）2）进行了说明。络合物为正方形平面，在溶液中易于解离。报告了类似的钯配合物，并讨论了硫醇钯[Pd（SR）2 ] n的结构。
• 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
• Roundhill, D. Max, Inorganic Chemistry, 1980, vol. 19, # 2, p. 557 - 560
  作者：Roundhill, D. Max

  DOI：——

  日期：——
• Preparation of diarylthiolatonickel(II) complexes, Ni(SAr)2L2, by oxidative addition of diaryl disulfides to Ni(0) complexes and Ni-catalyzed coupling reactions between thiophenols and aryl halides
  作者：Takakazu Yamamoto、Yasuhiro Sekine

  DOI：10.1016/s0020-1693(00)82371-3

  日期：1984.3