(1,8-bis(diphenylphosphino)-9,10-ethano-9,10-dihydroanthracene)Ni(η3-methallyl)BF4 | 1296195-05-5

• 英文名称: (1,8-bis(diphenylphosphino)-9,10-ethano-9,10-dihydroanthracene)Ni(η3-methallyl)BF4
• CAS: 1296195-05-5
• 化学式: BF₄*C₄₄H₃₉NiP₂
• 分子量: 775.236
• InChiKey: LDWARXPCYZPXDY-LXVUQTSPSA-N

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

• 作为产物：
  描述：

  1,8-bis(diphenylphosphino)-9,10-ethano-9,10-dihydroanthracene 以 四氢呋喃 为溶剂， 生成 (1,8-bis(diphenylphosphino)-9,10-ethano-9,10-dihydroanthracene)Ni(η3-methallyl)BF4
  参考文献：
  名称：

  Highly Efficient Nickel-Catalyzed 2-Methyl-3-butenenitrile Isomerization: Applications and Mechanistic Studies Employing the TTP Ligand Family

  摘要：

  A series of sterically and electronically fine-tuned, chelating diphosphine ligands were synthesized. The ligands are analogues of Triptyphos (TTP, 1), all based upon a variably 9,10-two-carbon-bridged 9,10-dihydroanthracene scaffold. These new TTP-type ligands were employed in the Ni(0)-catalyzed isomerization of 2-methyl-3-butenenitrile (2M3BN), one of the key steps of industrial adiponitrile production by the DuPont process. The reaction showed a surprising preference for ligands bearing electron-donating substituents, such as methoxy or methyl groups, in the phenyl para position of the Ni-ligating PPh2 units. Octyltriptyphos (3) afforded the highest 2M3BN-isomerization turnover rate yet reported. A series of deuterium-labeling experiments was performed to investigate the possibility of an isomerization mechanism consisting of a cascade of de- and rehydrocyanation steps, which could be excluded. Using the ethano-bridged ligand 4, complex 16a (4-kappa P:kappa P')Ni(eta(3)-C4H7)CN (supposedly an intermediate of the 2M3BN-isomerization reaction) was isolated, and its solid-state structure was determined by X-ray diffraction analysis. The complete catalytic cycle of 2M3BN isomerization with ligand 4, as suggested by the available experimental evidence, was modeled using DFT methods.

  DOI：

  10.1021/om200164f