palladium(II) (Ra,Ra)-N,N-bis(binaphthylphosphonito)phenylamine dichloride | 765277-42-7

• 英文名称: palladium(II) (Ra,Ra)-N,N-bis(binaphthylphosphonito)phenylamine dichloride
• CAS: 765277-42-7
• 化学式: C₄₆H₂₉Cl₂NO₄P₂Pd
• 分子量: 899.014
• InChiKey: ZSZZLJMCVABOFZ-UHFFFAOYSA-L

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：

  二(氰基苯)二氯化钯 、 (Ra,Ra)-N,N-di(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphthyl)phenylamine 以 甲苯 为溶剂， 以74%的产率得到palladium(II) (Ra,Ra)-N,N-bis(binaphthylphosphonito)phenylamine dichloride
  参考文献：
  名称：

  Rhodium( I ), Palladium( II ) and Platinum( II ) Coordination Chemistry of the Short‐Bite Chiral Ligands ( S _c )‐ N , N ‐Bis(diphenylphosphanyl)‐ sec ‐butylamine, ( R _a , R _a )‐ N , N ‐Bis(binaphthylphosphonito)phenylamine and ( R _a , S _c )‐ N ‐(Diphenylphosphanyl)‐ N ‐(binaphthylphosphonito)‐ sec ‐butylamine

  摘要：

  AbstractThe new short‐bite chiral ligands (Sc)‐N,N‐bis(diphenylphosphanyl)‐sec‐butylamine [(Sc)‐1], (Ra,Ra)‐N,N‐bis(binaphthylphosphonito)phenylamine [(Ra,Ra)‐2] and (Ra,Sc)‐N‐(diphenylphosphanyl)‐N‐(binaphthylphosphonito)‐sec‐butylamine [(Ra,Sc)‐3] have been treated with rhodium(I), palladium(II) and platinum(II) substrates. The (Sc)‐1 ligand reacts with [Pd(C6H5CN)2Cl2], [Pt(COD)Cl2] and [Rh(COD)(THF)2]PF6 to afford the products [Pd(Sc‐1)Cl2] (4), [Pt(Sc‐1)Cl2] (5) and [Rh(COD)(Sc‐1)]PF6 (6), respectively, in high yields. By bubbling CO to a CH2Cl2 solution of 6, we formed the dicarbonyl species [Rh(CO)2(Sc‐1)]PF6 (7), which is stable only in solution under CO. Compounds 4 and 5 were characterized additionally by X‐ray diffraction studies. The ligand (Ra,Ra)‐2 reacts with [Pd(C6H5CN)2Cl2] and [Pt(COD)I2] to give [Pd(Ra,Ra‐2)Cl2] (8) and [Pt(Ra,Ra‐2)I2] (9), respectively; the reaction with [Rh(CO)2Cl]2 or [Rh(COD)(THF)2]PF6 affords a mixture of mono‐ and binuclear compounds, in which the ligand is oxidized to the corresponding phosphonate or is partially hydrolysed. The compounds [Pd(Ra,Sc‐3)Cl2] (10) and [Pt(Ra,Sc‐3)I2] (11) were obtained in the analogous reactions using the asymmetric (Ra,Sc)‐3 ligand. This ligand reacted with [Rh(CO)2Cl]2 in a 2:1 molar ratio in hexane to give a mixture of products in almost equal amounts. The 31P{1H} NMR spectrum recorded in CDCl3 allowed us to identify the chelate [Rh(Ra,Sc‐3)(CO)Cl] (12); the nature of the accompanying dinuclear species 13 is not clear. The catalytic systems formed by [Rh(acac)(CO)2] and the ligands (Ra,Ra)‐2 and (Ra,Sc)‐3, at ligand/metal ratios of 1:1 and 1:2, were unstable under the experimental conditions used (CO/H2 pressure of 50 atm and temperature of 40 °C) for the hydroformylation of styrene; instead, metallic rhodium was afforded together with unidentified decomposition products. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

  DOI：

  10.1002/ejic.200300568