二氯{（1R，2R）-N，N-双[2-（二苯基膦基）苄基]环己烷-1，2-二胺}钌（II） | 429678-11-5

• 物质功能分类: 有机原料 - 氨基化合物
• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 二氯{（1R，2R）-N，N-双[2-（二苯基膦基）苄基]环己烷-1，2-二胺}钌（II）
• 中文别名: [(1R,2R)-N,N-双[2-(二苯基膦)苄基]环己烷-1,2-二胺]二氯化钌；苄二氯{(1R,2R)- N,N -双[2 - (二苯基膦)]环己烷-1,2 - 二胺钌(II)
• 英文名称: trans-[RuCl2(κ4-(1R,2R)-N,N'-bis[2-(diphenylphosphanyl)-benzylidene]-1,2-diaminocyclohexane)]
• 英文别名: Dichloro{(1R,2R)-N,N-bis[2-(diphenylphosphino)benzyl]cyclohexane-1,2-diamine}ruthenium(II)；(1R,2R)-1-N,2-N-bis[(2-diphenylphosphanylphenyl)methyl]cyclohexane-1,2-diamine;ruthenium(2+);dichloride
• CAS: 429678-11-5
• 化学式: C₄₄H₄₄Cl₂N₂P₂Ru
• 分子量: 834.77
• InChiKey: ARUWPYVEQOFGTQ-KGDVQYBBSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  51
• 可旋转键数：
  12
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  24.1
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  silver tetrafluoroborate 、 二氯{（1R，2R）-N，N-双[2-（二苯基膦基）苄基]环己烷-1，2-二胺}钌（II） 、 二氯甲烷 、 水 、 乙腈 以 乙腈 为溶剂， 以90%的产率得到cis-[RuCl(acetonitrile)(κ4-(1R,2R)-N,N'-bis[2-(diphenylphosphanyl)-benzylidene]-1,2-diaminocyclohexane)]BF4*CH2Cl2*2H2O
  参考文献：
  名称：

  Synthesis of Chiral Cationic (Diimino‐ and diaminodiphosphane)ruthenium Complexes and Their Applications in Catalytic Oxidation − Crystal Structures of cis ‐[RuCl(py){κ ⁴ ‐Ph ₂ PC ₆ H ₄ CH=NC ₆ H ₁₀ N=CHC ₆ H ₄ PPh ₂ }]BF ₄ and cis ‐[RuCl(py){κ ⁴ ‐Ph ₂ PC ₆ H ₄ CH=NC ₆ H ₁₀ N(H)CH ₂ C ₆ H ₄ PPh ₂ }]BF ₄

  摘要：

  AbstractHalide abstraction of trans‐[RuCl2{κ4‐(1R,2R)‐PNNP}] {(1R,2R)‐PNNP = (1R,2R)‐N,N′‐bis[2‐(diphenylphosphanyl)benzylidene]‐1,2‐diiminocyclohexane} and trans‐[RuCl2{κ4‐(1R,2R)‐P(NH)(NH)P}] {(1R,2R)‐P(NH)(NH)P = (1R,2R)‐N,N′bis[2‐(diphenylphosphanyl)benzylidene]‐1,2‐diaminocyclohexane} with AgBF4 in acetonitrile at ambient temperature gave cis‐[RuCl(CH3CN){κ4‐(1R,2R)‐PNNP}][BF4] (1) and cis‐[RuCl(CH3CN){κ4‐(1R,2R)‐P(NH)(NH)P}][BF4] (2), respectively. When 1 was refluxed in pyridine (py), the coordinated CH3CN was replaced by pyridine to form cis‐[RuCl(py){κ4‐(1R,2R)‐PNNP}][BF4] (3). However, when 2 was refluxed in pyridine, one of the amino moieties (−CH2−NH−)was oxidized to an imino moiety (−CH=N−) with concomitant displacement of the coordinated CH3CN by pyridine to produce cis‐[RuCl(py){κ4‐(1R,2R)‐P(N)(NH)P}][BF4] (4). The structures of 3 and 4 were ascertained by X‐ray crystallography. Compounds 1−4 are effective catalysts for the epoxidation of various olefins with air. A turnover frequency of up to 733 h−1 and an enantiomeric excess of up to 24% were obtained for the epoxidation of styrene catalysed by 2. Compound 2 can also catalyse the epoxidation, dehydrogenation and C−H activation of various olefins, alcohols and alkanes by tert‐butyl hydroperoxide with high chemical selectivity. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  DOI：

  10.1002/ejic.200300238