[bis(triphenylphosphoranylidene)ammonium][NiCl(P(o-C6H3-3-SiMe3-2-S)2(o-C6H3-3-SiMe3-2-SH))] | 956107-44-1

• 英文名称: [bis(triphenylphosphoranylidene)ammonium][NiCl(P(o-C6H3-3-SiMe3-2-S)2(o-C6H3-3-SiMe3-2-SH))]
• 英文别名: [PPN][NiCl(P(o-C6H3-3-SiMe3-2-S)2(o-C6H3-3-SiMe3-2-SH))]
• CAS: 956107-44-1
• 化学式: C₂₇H₃₇ClNiPS₃Si₃*C₃₆H₃₀NP₂
• 分子量: 1205.75
• InChiKey: BGXAKNLRFIGOCE-UHFFFAOYSA-K

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
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• 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：

  [bis(triphenylphosphoranylidene)ammonium][NiCl(P(o-C6H3-3-SiMe3-2-S)2(o-C6H3-3-SiMe3-2-SH))] 在 2,4,6-tri-tert-butylphenoxyl 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 生成
  参考文献：
  名称：

  从硫醇盐结合的 Ni(III) 氢化物释放 H2

  摘要：

  末端 NiIII 氢化物是由分子电催化剂和金属酶催化的质子还原的中间体，但顺磁性镍氢化物配合物的明确例子主要限于桥连氢化物。在此，我们报告了 S = ½、末端结合的硫醇盐-NiIII-H 复合物的合成。该物种，特别是其末端氢化物配体，已经通过振动和 EPR 技术（包括脉冲 EPR 研究）进行了彻底的表征。相应的 DFT 计算表明在硫醇盐配体上有明显的自旋泄漏。与硫醇盐-NiIII-H 物种的末端氢化物配体的超精细偶联与为 Ni-C 氢化酶中间体 (NiIII-H-FeII) 提出的氢化物配体相当。升温后，特色的硫醇盐-NiIII-H 物种经历了 H2 的双分子还原消除。讨论了相关的动力学研究，并与最近报道的结构相关的 FeIII-H 物种进行了双分子 HH 偶联进行了比较。

  DOI：

  10.1021/jacs.0c00712
• 作为产物：
  描述：

  [PPN][NiCl4] 、 2,2',2"-trimercapto-3,3',3"-tris(trimethylsilyl)triphenylphosphine 以 四氢呋喃 、 乙腈 为溶剂， 以65%的产率得到[bis(triphenylphosphoranylidene)ammonium][NiCl(P(o-C6H3-3-SiMe3-2-S)2(o-C6H3-3-SiMe3-2-SH))]
  参考文献：
  名称：

  Mononuclear Ni(II)-Thiolate Complexes with Pendant Thiol and Dinuclear Ni(III/II)-Thiolate Complexes with Ni···Ni Interaction Regulated by the Oxidation Levels of Nickels and the Coordinated Ligands

  摘要：

  Compared to [Ni-II(SePh)(P(o-C6H3-3-SiMe3-2-S)(2)(o-C6H3-3-SiMe3-2-SH))](-) (1a) and [Ni-II(Cl)(P(o-C6H3-3-SiMe3-2-S)(2)(o-C6H3-3-SiMe3-2-SH))](-) (3a) with a combination of the intramolecular [Ni center dot center dot center dot H-S] and [Ni-S center dot center dot center dot H-S] interactions, complexes (Ni-II(SePh)(P(o-C6H3-3-Sime(3)-2-S)(2)(o-C6H3-3-SiMe3-2-SH))](-) (1b) and [Ni-II(Cl)(P (o-C6H3-3-SiMe3-2-S)(2)(o-C6H3-3-SiMe3-2-SH))](-) (3b) with intramolecular [Ni center dot center dot center dot H-S] interaction exhibit lower nu(S-H) stretching frequencies (2137 and 2235 cm(-1) for 1b and 3b vs 2250 and 2287 cm(-1) for 1a and 3a, respectively) and smaller torsion angles (27.20 for 3b vs 58.9 and 59.1 degrees for 1a and 3a, respectively). The pendant thiol interaction modes of 1a, 3a, and 3b in the solid state are controlled by the solvent pairs of crystallization. Oxygen oxidation of dinuclear [Ni-II(P(o-C6H3-3-SiMe3-2-S)(2)(o-C6H3-3-SiMe3-2-SH))](2) (4) yielded thermally stable dinuclear [Ni-III(P(o-C6H3-3-SiMe3-2S)(2)(o-C6H3-3-SiMe3-2-mu-S))](2) (5). The two paramagnetic d(7) Ni-II cores (S = 1/2) with antiferromagnetic coupling (J = -3.13 cm(-1)) rationalize the diamagnetic property of 5. The fully delocalized mixed-valence [Ni(II)-Ni(III)] complexes [Ni-2(P(o-C6H3-3-SiMe3-2-S)(3))(2)](-) (6) and [Ni-2(P(o-C6H3-3-SiMe3-2-S)(3))(P(o-C6H3-3-SiMe3-2-S)(2)(o-C6H3-3-siMe(3)-2-SCH3))] (7) were isolated upon the reduction of 5 and the methylation of 6, respectively. The electronic perturbation from the sulfur methylation of 6 triggers the stronger Ni center dot center dot center dot Ni interaction and the geometrical rearrangement from the diamond shape of the [NiS2Ni] core to the butterfly structure of [Ni(mu-S)(2)Ni] to yield 7 with Ni center dot center dot center dot Ni distances of 2.6088(1) angstrom. The distinctly different Ni center dot center dot center dot Ni distances (2.6026(7) for 5 and 2.8289(15) angstrom for 6) and the coordination number of the nickels indicate a balance of geometrical requirements for different oxidation levels of [PS3Ni-NiPS3] cores of 5 and 6.

  DOI：

  10.1021/ic700719h