[Ni(PhP(C2H4PPh2)2)(2-pyridinethiolate)]BPh4 | 1263217-14-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [Ni(PhP(C2H4PPh2)2)(2-pyridinethiolate)]BPh4
• 英文别名: bis(2-diphenylphosphanylethyl)-phenylphosphane;nickel(2+);pyridine-2-thiolate;tetraphenylboranuide
• CAS: 1263217-14-6
• 化学式: C₂₄H₂₀B*C₃₉H₃₇NNiP₃S
• 分子量: 1022.64
• InChiKey: IEIWQBASPLSYBE-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  11.11
• 重原子数：
  70
• 可旋转键数：
  9
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  13.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,6-lutidinium tetraphenylborate 、 [Ni(PhP(C2H4PPh2)2)(2-pyridinethiolate)]BPh4 以 乙腈 为溶剂， 生成 [Ni(PhP(C2H4PPh2)2)(2-pyridinethiol)](2+)
  参考文献：
  名称：

  Kinetic and Theoretical Studies on the Protonation of [Ni(2-SC₆H₄N){PhP(CH₂CH₂PPh₂)₂}]⁺: Nitrogen versus Sulfur as the Protonation Site

  摘要：

  The complexes [Ni(4-Spy)(triphos)]BPh4 and [Ni(2-Spy)(triphos)]BPh4 {triphos = PhP(CH2CH2PPh2)(2), 4-Spy = 4-pyridinethiolate, 2-Spy = 2-pyridinethiolate} have been prepared and characterized both spectroscopically and using X-ray crystallography. In both complexes the triphos is a tridentate ligand. However, [Ni(4-Spy)(triphos)](+) comprises a 4-coordinate, square-planar nickel with the 4-Spy ligand bound to the nickel through the sulfur while [Ni(2-Spy)(triphos)](+) contains a 5-coordinate, trigonal-bipyramidal nickel with a bidentate 2-Spy ligand bound to the nickel through both sulfur and nitrogen. The kinetics of the reactions of [Ni(4-Spy)(triphos)](+) and [Ni(2-Spy)(triphos)](+) with lutH(+) (lut = 2,6-dimethylpyridine) in MeCN have been studied using stopped-flow spectrophotometry, and the two complexes show very different reactivities. The reaction of [Ni(4-Spy)(triphos)](+) with lutH(+) is complete within the deadtime of the stopped-flow apparatus (2 ms) and corresponds to protonation of the nitrogen. However, upon mixing [Ni(2-Spy)(triphos)](+) and lutH(+) a reaction is observed (on the seconds time scale) to produce an equilibrium mixture. The mechanistic interpretation of the rate law has been aided by the application of MSINDO semiempirical and ADF calculations. The kinetics and calculations are consistent with the reaction between [Ni(2-Spy)(triphos)](+) and lutH(+) involving initial protonation of the sulfur followed by dissociation of the nitrogen and subsequent transfer of the proton from sulfur to nitrogen. The factors affecting the position of protonation and the coupling of the coordination state of the 2-pyridinethiolate ligand to the site of protonation are discussed.

  DOI：

  10.1021/ic101444d
• 作为产物：
  描述：

  [bis(2-diphenylphosphinoethyl)phenylphosphine]chloronickel(II) tetraphenylborate 、 2-巯基吡啶钠盐 以 四氢呋喃 为溶剂， 以26%的产率得到[Ni(PhP(C2H4PPh2)2)(2-pyridinethiolate)]BPh4
  参考文献：
  名称：

  Kinetic and Theoretical Studies on the Protonation of [Ni(2-SC₆H₄N){PhP(CH₂CH₂PPh₂)₂}]⁺: Nitrogen versus Sulfur as the Protonation Site

  摘要：

  The complexes [Ni(4-Spy)(triphos)]BPh4 and [Ni(2-Spy)(triphos)]BPh4 {triphos = PhP(CH2CH2PPh2)(2), 4-Spy = 4-pyridinethiolate, 2-Spy = 2-pyridinethiolate} have been prepared and characterized both spectroscopically and using X-ray crystallography. In both complexes the triphos is a tridentate ligand. However, [Ni(4-Spy)(triphos)](+) comprises a 4-coordinate, square-planar nickel with the 4-Spy ligand bound to the nickel through the sulfur while [Ni(2-Spy)(triphos)](+) contains a 5-coordinate, trigonal-bipyramidal nickel with a bidentate 2-Spy ligand bound to the nickel through both sulfur and nitrogen. The kinetics of the reactions of [Ni(4-Spy)(triphos)](+) and [Ni(2-Spy)(triphos)](+) with lutH(+) (lut = 2,6-dimethylpyridine) in MeCN have been studied using stopped-flow spectrophotometry, and the two complexes show very different reactivities. The reaction of [Ni(4-Spy)(triphos)](+) with lutH(+) is complete within the deadtime of the stopped-flow apparatus (2 ms) and corresponds to protonation of the nitrogen. However, upon mixing [Ni(2-Spy)(triphos)](+) and lutH(+) a reaction is observed (on the seconds time scale) to produce an equilibrium mixture. The mechanistic interpretation of the rate law has been aided by the application of MSINDO semiempirical and ADF calculations. The kinetics and calculations are consistent with the reaction between [Ni(2-Spy)(triphos)](+) and lutH(+) involving initial protonation of the sulfur followed by dissociation of the nitrogen and subsequent transfer of the proton from sulfur to nitrogen. The factors affecting the position of protonation and the coupling of the coordination state of the 2-pyridinethiolate ligand to the site of protonation are discussed.

  DOI：

  10.1021/ic101444d