cis-ReOMe2(2,2'-bipyridine)CH2SiMe3 | 366478-24-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: cis-ReOMe2(2,2'-bipyridine)CH2SiMe3
• 英文别名: trans-ReOMe2(2,2'-bipyridine)CH2SiMe3
• CAS: 366478-24-2；366489-25-0
• 化学式: C₁₆H₂₅N₂OReSi
• 分子量: 475.68
• InChiKey: CPSMIJLFRKYPOI-UHFFFAOYSA-N

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：
  None

反应信息

• 作为反应物：
  描述：

  盐酸 、 cis-ReOMe2(2,2'-bipyridine)CH2SiMe3 、 cis-ReOMe2(2,2'-bipyridine)CH2SiMe3 以 二氯甲烷 为溶剂， 以90%的产率得到ReOMe(2,2'-bipyridine)(CH2SiMe3)Cl
  参考文献：
  名称：

  Synthesis, characterization and reactivity of ReOMe2(bipy)X complexes

  摘要：

  The complexes cis- and trans-ReOMe2(bipy)Cl, where cis or trans refers to the Me-Re-Me regiochemistry, were observed to react as follows: (1) with the alkylating agents RMgCl (R = CH2SiMe3 and CH2Ph) and RLi (R = Me) to give ReOMe2(bipy)R, and (2) with the alkoxides NaOR ' (R '= Me and Et) to give trans -ReOMe2(bipy)(OR '). The complex ReoMe(2)(bipy)CH2SiMe3 was observed by H-1 NMR spectroscopy to undergo trans to cis isomerization, which proceeded via reversible first-order kinetics, with DeltaH degrees = 1.60(4) kcal mol (-1) and DeltaS degrees = 3.7(1) eu. At room temperature, DeltaG degrees = 0.5(1) kcal mol (-1) and K-eq = 0.42(2), indicating a weak thermodynamic preference for the trans isomer. The activation parameters for the trans to cis isomerization were DeltaH(double dagger) = 26(2) kcal mol (-1) and DeltaS(double dagger) (1) = 10(7) eu, and those for the reverse cis to trans isomerization were DeltaH(double dagger) (-1) = 27(2) kcal mol(-1) and DeltaS(double dagger) (-1) = 14(7) eu. Treatment of a mixture of cis- and trans -ReOMe2(bipy)CH2SiMe3 with anhydrous HCl gave ReOMe(bipy)(CH2SiMe3)Cl; similar treatment of ReOMe3(bipy) and ReOMe2(bipy)CH2Ph gave cis-ReOMe2(bipy)Cl. Exposure of ReOMe(bipy)(CH2SiMe3)Cl to AgPF6 in acetonitrile-d(3) gave the cationic nitrile adduct [ReOMe(bipy)(CH2SiMe3)(CD3CN)][PF6]. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(01)00745-8
• 作为产物：
  描述：

  cis-ReOMe2(2,2'-bipyridine)Cl 、 cis-ReOMe2(2,2'-bipyridine)Cl 、 (三甲基硅基)甲基氯化镁 以 乙醚 为溶剂， 以30%的产率得到cis-ReOMe2(2,2'-bipyridine)CH2SiMe3
  参考文献：
  名称：

  Synthesis, characterization and reactivity of ReOMe2(bipy)X complexes

  摘要：

  The complexes cis- and trans-ReOMe2(bipy)Cl, where cis or trans refers to the Me-Re-Me regiochemistry, were observed to react as follows: (1) with the alkylating agents RMgCl (R = CH2SiMe3 and CH2Ph) and RLi (R = Me) to give ReOMe2(bipy)R, and (2) with the alkoxides NaOR ' (R '= Me and Et) to give trans -ReOMe2(bipy)(OR '). The complex ReoMe(2)(bipy)CH2SiMe3 was observed by H-1 NMR spectroscopy to undergo trans to cis isomerization, which proceeded via reversible first-order kinetics, with DeltaH degrees = 1.60(4) kcal mol (-1) and DeltaS degrees = 3.7(1) eu. At room temperature, DeltaG degrees = 0.5(1) kcal mol (-1) and K-eq = 0.42(2), indicating a weak thermodynamic preference for the trans isomer. The activation parameters for the trans to cis isomerization were DeltaH(double dagger) = 26(2) kcal mol (-1) and DeltaS(double dagger) (1) = 10(7) eu, and those for the reverse cis to trans isomerization were DeltaH(double dagger) (-1) = 27(2) kcal mol(-1) and DeltaS(double dagger) (-1) = 14(7) eu. Treatment of a mixture of cis- and trans -ReOMe2(bipy)CH2SiMe3 with anhydrous HCl gave ReOMe(bipy)(CH2SiMe3)Cl; similar treatment of ReOMe3(bipy) and ReOMe2(bipy)CH2Ph gave cis-ReOMe2(bipy)Cl. Exposure of ReOMe(bipy)(CH2SiMe3)Cl to AgPF6 in acetonitrile-d(3) gave the cationic nitrile adduct [ReOMe(bipy)(CH2SiMe3)(CD3CN)][PF6]. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(01)00745-8