[Ni(P(o-C6H3-3-SiMe3-2-S)2(o-C6H3-3-SiMe3-2-SH))]2 | 956107-45-2

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: [Ni(P(o-C6H3-3-SiMe3-2-S)2(o-C6H3-3-SiMe3-2-SH))]2
• 英文别名: nickel(2+);2-[(2-sulfanyl-3-trimethylsilylphenyl)-(2-sulfido-3-trimethylsilylphenyl)phosphanyl]-6-trimethylsilylbenzenethiolate
• CAS: 956107-45-2
• 化学式: C₅₄H₇₄Ni₂P₂S₆Si₆
• 分子量: 1263.42
• InChiKey: AHYNWFYJRSXLMT-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  10.36
• 重原子数：
  70
• 可旋转键数：
  8
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  6
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [Ni(P(o-C6H3-3-SiMe3-2-S)2(o-C6H3-3-SiMe3-2-SH))]2 在 O₂ 作用下， 以 正己烷 为溶剂， 以60%的产率得到[Ni(P(o-C6H3-3-SiMe3-2-S)3)]2
  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
• 作为产物：
  描述：

  [bis(triphenylphosphoranylidene)ammonium][Ni(SePh)(P(o-C6H3-3-SiMe3-2-S)2(o-C6H3-3-SiMe3-2-SH))] 在 [(C₂H₅)3O][BF₄] 作用下， 以 四氢呋喃 为溶剂， 以70%的产率得到[Ni(P(o-C6H3-3-SiMe3-2-S)2(o-C6H3-3-SiMe3-2-SH))]2
  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