dicarbonyldichlorobis(2,8-bis[2-(diphenylphosphino)ethylthio]-4,10-dimethyl-6H,12H-5,11-methanodibenzo[b,f]diazocine)dirhodium(I) | 881735-96-2

• 英文名称: dicarbonyldichlorobis(2,8-bis[2-(diphenylphosphino)ethylthio]-4,10-dimethyl-6H,12H-5,11-methanodibenzo[b,f]diazocine)dirhodium(I)
• CAS: 881735-96-2
• 化学式: C₉₂H₈₈Cl₂N₄O₂P₄Rh₂S₄
• 分子量: 1810.61
• InChiKey: HDENVTZFBCBVSW-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 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：

  tetrakis(2,8-bis[2-(diphenylphosphino)ethylthio]-4,10-dimethyl-6H,12H-5,11-methanodibenzo[b,f]diazocine)tetrarhodium(I) tetrakis[3,5-bis(trifluoromethyl)phenyl]borate 、 tris(2,8-bis[2-(diphenylphosphino)ethylthio]-4,10-dimethyl-6H,12H-5,11-methanodibenzo[b,f]diazocine)trirhodium(I) tetrakis[3,5-bis(trifluoromethyl)phenyl]borate 、 一氧化碳 、 苄基三乙基氯化铵 以 二氯甲烷-D2 为溶剂， 生成 tetracarbonyltetrachlorotetrakis(2,8-bis[2-(diphenylphosphino)ethylthio]-4,10-dimethyl-6H,12H-5,11-methanodibenzo[b,f]diazocine)tetrarhodium(I) 、 dicarbonyldichlorobis(2,8-bis[2-(diphenylphosphino)ethylthio]-4,10-dimethyl-6H,12H-5,11-methanodibenzo[b,f]diazocine)dirhodium(I) 、 tricarbonyltrichlorotris(2,8-bis[2-(diphenylphosphino)ethylthio]-4,10-dimethyl-6H,12H-5,11-methanodibenzo[b,f]diazocine)trirhodium(I)
  参考文献：
  名称：

  Metallomacrocycles Incorporating a Hemilabile Tröger's Base Derived Ligand

  摘要：

  Troger's base, a chiral molecule with a rigid 900 backbone, has been incorporated into a novel hemilabile phosphinoalkyl thioether ligand. Using the Weak Link Approach, this ligand has been reacted with Cu(CH3CN)(4)PF6 and [Rh(COE)(2)Cl](x) (COE = cyclooctene) to form metallomacrocycles. Upon reaction of the ligand with Cu-I, which prefers a tetrahedral coordination geometry, a bimetallic macrocycle was formed. Alternatively, owing to the steric restrictions imposed by the 900 backbone of the ligand and the square-planar geometry of Rh-I, when the ligand was reacted with [Rh(COE)(2)CI](x), the formation of bimetallic closed macrocycles was not observed, and instead a mixture of tri- and tetrametallic closed macrocycles is formed. Introducing pyridine to the Cu-I complex causes the weak thioether-Cu bonds to break, generating a large bimetallic open macrocycle. Upon reaction of the mixture of Rh-I metallornacrocycles with CO and CI-, the cyclic structure of these complexes becomes flexible enough that the dimeric bimetallic macrocycle forms, along with tri- and tetrameric open complexes. The mixture of differently sized Rh-I macrocyclic complexes has been analyzed using gel permeation chromatography, and the tetramer has been characterized by a single-crystal X-ray diffraction study. These are the first examples of metallomacrocycles containing a Troger's base derivative.

  DOI：

  10.1021/ic052000b