[(1,2-bis(diisopropylphosphino)ethane)Ni(κ2-S,C-SCH=CHCH=C(CN)] | 1243575-22-5

• 分子结构分类: 有机化合物 - 叠烯
• 英文名称: [(1,2-bis(diisopropylphosphino)ethane)Ni(κ2-S,C-SCH=CHCH=C(CN)]
• CAS: 1243575-22-5
• 化学式: C₁₉H₃₅NNiP₂S
• 分子量: 430.197
• InChiKey: WQUKEHJOWMJTNK-FMFSYIAASA-M

计算性质

• 辛醇/水分配系数(LogP)：
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• 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：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [(1,2-bis(diisopropylphosphino)ethane)Ni(κ2-S,C-SCH=CHCH=C(CN)] 以 氘代四氢呋喃 为溶剂， 以74%的产率得到[(1,2-bis(diisopropylphosphino)ethane)Ni(CN)(2-thiophene)]
  参考文献：
  名称：

  Competitive Carbon−Sulfur vs Carbon−Carbon Bond Activation of 2-Cyanothiophene with [Ni(dippe)H]₂

  摘要：

  The processes of C C and C S bond cleavage have been studied with the homogeneous organometallic compound [Ni(dippe)H](2) (1). When 1 is reacted with 2-cyanothiophene at room temperature, cleavage of the nitrile-substituted C S bond occurs, forming the Ni-metallacycle complex (dippe)Ni(kappa(2)-S,C-SCH=CHCH=C(CN)) (2a), which has been fully characterized by NMR spectroscopy and X-ray diffraction. 2a was converted to the C CN cleavage product (dippe)Ni(CN)(2-thiophenyl) (3) when heated in solution. On closer inspection, four other intermediates were observed by P-31 NMR spectroscopy at low temperature. Structures for the intermediates were elucidated through a combination of independent synthesis, theoretical calculations, chemical characterization, and experimental precedent. A kinetic product (dippe)Ni(kappa(2)-S,C-SC(CN)=CHCH=CH) (2b) was formed from cleavage of the nonsubstituted C S bond, as well as a Ni(0) eta(2)-nitrile intermediate, (dippe)Ni(eta(2)-C,N-2-cyanothiophene) (4), and a dinuclear mixed Ni(0) Ni(II) product (6b). A complete DFT analysis of this system has been carried out to reveal comparative details about the two bond cleavage transition states.

  DOI：

  10.1021/ja104158h
• 作为产物：
  描述：

  2-氰基噻吩 、 ((1,2-bis(diisopropylphosphino)ethane)NiH)2 以 四氢呋喃 为溶剂， 以93%的产率得到[(1,2-bis(diisopropylphosphino)ethane)Ni(κ2-S,C-SCH=CHCH=C(CN)]
  参考文献：
  名称：

  Competitive Carbon−Sulfur vs Carbon−Carbon Bond Activation of 2-Cyanothiophene with [Ni(dippe)H]₂

  摘要：

  The processes of C C and C S bond cleavage have been studied with the homogeneous organometallic compound [Ni(dippe)H](2) (1). When 1 is reacted with 2-cyanothiophene at room temperature, cleavage of the nitrile-substituted C S bond occurs, forming the Ni-metallacycle complex (dippe)Ni(kappa(2)-S,C-SCH=CHCH=C(CN)) (2a), which has been fully characterized by NMR spectroscopy and X-ray diffraction. 2a was converted to the C CN cleavage product (dippe)Ni(CN)(2-thiophenyl) (3) when heated in solution. On closer inspection, four other intermediates were observed by P-31 NMR spectroscopy at low temperature. Structures for the intermediates were elucidated through a combination of independent synthesis, theoretical calculations, chemical characterization, and experimental precedent. A kinetic product (dippe)Ni(kappa(2)-S,C-SC(CN)=CHCH=CH) (2b) was formed from cleavage of the nonsubstituted C S bond, as well as a Ni(0) eta(2)-nitrile intermediate, (dippe)Ni(eta(2)-C,N-2-cyanothiophene) (4), and a dinuclear mixed Ni(0) Ni(II) product (6b). A complete DFT analysis of this system has been carried out to reveal comparative details about the two bond cleavage transition states.

  DOI：

  10.1021/ja104158h