[(4-(dicyclohexylphosphino)-N,N-dimethylpiperidinium)Ni(CO)3]Cl | 181864-91-5

• 英文名称: [(4-(dicyclohexylphosphino)-N,N-dimethylpiperidinium)Ni(CO)3]Cl
• CAS: 181864-91-5
• 化学式: C₂₂H₃₇NNiO₃P*Cl
• 分子量: 488.657
• InChiKey: PKGDKDWEWIHBTO-UHFFFAOYSA-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

• 作为产物：
  描述：

  4-(dicyclohexylphosphino)-N,N-dimethylpiperidinium chloride 、 tetracarbonyl nickel 以 二氯甲烷 为溶剂， 生成 [(4-(dicyclohexylphosphino)-N,N-dimethylpiperidinium)Ni(CO)3]Cl
  参考文献：
  名称：

  Experimental and Computational Study of Steric and Electronic Effects on the Coordination of Bulky, Water-Soluble Alkylphosphines to Palladium under Reducing Conditions:  Correlation to Catalytic Activity

  摘要：

  Sterically demanding, water-soluble alkylphosphine ligands 2-(di-tert-butylphosphino)ethyltrimethylammonium chloride (t-Bu-Amphos) and 4-(di-tert-butylphosphino)-N,N-di-methylpiperidinium chloride (t-Bu-Pip-phos) in combination with palladium salts provided active catalysts for the cross-coupling of aryl halides under mild conditions in aqueous solvents, whereas 4-(dicyclohexylphosphino)-N,N-dimethylpiperidinium chloride (Cy-Pip-phos) gave a less active catalyst. Catalyst activity increased with increasing cone angle of the ligands, but the chi electronic parameter determined from the symmetric C-O stretching frequency of LNi(CO)(3) did not correlate with catalyst activity. Catalyst activity correlated with other calculated electronic parameters, such as the HOMO-LUMO energy gap of the ligand and the HOMO energy level of the LPd(0) species. Multinuclear NMR spectroscopic studies showed that t-Bu-Amphos and t-Bu-Pip-phos rapidly form L2Pd(0) (L = t-Bu-Amphos or t-Bu-Pip-phos) complexes when reacted with Pd(OAc)(2) under reducing conditions over a range of L:Pd ratios. In contrast, the coordination chemistry of Cy-Pip-phos depended on the Cy-Pip-phos:Pd ratio. At a less than or equal to 1: 1 Cy-Pip-phos:Pd ratio, rapid formation of L2Pd(0) occurred. At higher L:Pd ratios, initial formation of trans-(Cy-Pip-phos)(2)PdCl2 was observed followed by slow reduction to the Pd(0) complex.

  DOI：

  10.1021/om049241w

文献信息

• Synthesis of Water-Soluble, Aliphatic Phosphines and Their Application to Well-Defined Ruthenium Olefin Metathesis Catalysts
  作者：Bernhard Mohr、David M. Lynn、Robert H. Grubbs

  DOI：10.1021/om9603373

  日期：1996.10.1

  Water-soluble aliphatic phosphines Cy(2)P(CH2)(2)N(CH3)(3)Cl-+(-) (14), Cy(2)P[4-(N,N-dimethyl-piperidinium)]Cl-+(-) (15), Cy(2)P(CH2)(2)SO3-Na+ (16), and CyP[(CH2)(2)N(CH3)(3)Cl-+(-)](2) (17) (Cy = cyclohexyl) were prepared from air-stable, borane-protected precursors. Spectroscopic investigations of corresponding Pd(PR(3))(2)Cl-2 complexes were used to estimate the steric parameters of these new phosphines. Spectroscopic investigation of Ni(CO)(3)PR(3) complexes of the new phosphines indicated that phosphines bearing quaternary amine functionalities were less electron donating than tricyclohexylphosphine, while the presence of a sulfonate group increased phosphine electron donation. Cationic phosphines 14 and 15 were used to synthesize water-soluble ruthenium carbene complexes of the type (Cy(2)PR)(2)Cl2Ru=CHPh. These complexes initiate the ring-opening metathesis polymerization (ROMP) of functionalized 7-oxanorbornenes in water, methanol, and aqueous emulsions.