Fe(II)(CCCCCCSiMe₃)(dppe)Cp* | 1397970-67-0

• 英文名称: Fe(II)(CCCCCCSiMe₃)(dppe)Cp*
• CAS: 1397970-67-0
• 化学式: C₄₅H₄₈FeP₂Si
• 分子量: 734.756
• InChiKey: WYQKDJWCMAHYDY-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：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  ferrocenium hexafluorophosphate 、 Fe(II)(CCCCCCSiMe₃)(dppe)Cp* 以 二氯甲烷 为溶剂， 生成 [Fe(III)(CCCCCCSiMe₃)(dppe)Cp*]PF₆
  参考文献：
  名称：

  Iron and Ruthenium σ-Polyynyls of the General Formula [{M(dppe)Cp*}–(C≡C)_n–R]^0/+ (M = Fe, Ru): An Experimental and Theoretical Investigation

  摘要：

  Two series of metal-polyynyl complexes of iron and ruthenium of general formula [{M(dppe)Cp*}-(C C)(n)-R](0/+) (M = Fe, Ru; R = H, Ph, SiMe3, Au(PPh3); n = 1-3), have been synthesized, characterized, and theoretically analyzed. The results provide a comprehensive description of the effect of the length of the conjugated carbon chain and the role of the nature of the metal atom and the terminal substituent on their neutral and oxidized states. For the latter, the spin density found on the carbon chain is a source of instability; e.g., for R = Au(PPh3), the oxidized compounds are much more accessible electrochemically than the rest of the series but are susceptible to radical attack. Of particular interest is the use of joint experimental and theoretical EPR studies, which allow elucidation of the differences of behavior within the two series. It reveals that the atomic spin density on the metal is not a sufficient criterion to evaluate EPR anisotropy but that the specific nodal properties of the frontier spin-orbitals highly influence the EPR components. The localization of the spin density on specific carbon atoms of the conjugated chain (even numbered) opens up the possibility of building extended systems by targeted radical reactions.

  DOI：

  10.1021/om300584u
• 作为产物：
  描述：

  1-碘-2-三甲基硅基乙炔 、 Fe(II){CCCCAu(PPh₃)}(dppe)Cp* 在 copper(l) iodide 、 四(三苯基膦)钯 作用下， 以 四氢呋喃 、 三乙胺 为溶剂， 以55%的产率得到Fe(II)(CCCCCCSiMe₃)(dppe)Cp*
  参考文献：
  名称：

  Iron and Ruthenium σ-Polyynyls of the General Formula [{M(dppe)Cp*}–(C≡C)_n–R]^0/+ (M = Fe, Ru): An Experimental and Theoretical Investigation

  摘要：

  Two series of metal-polyynyl complexes of iron and ruthenium of general formula [{M(dppe)Cp*}-(C C)(n)-R](0/+) (M = Fe, Ru; R = H, Ph, SiMe3, Au(PPh3); n = 1-3), have been synthesized, characterized, and theoretically analyzed. The results provide a comprehensive description of the effect of the length of the conjugated carbon chain and the role of the nature of the metal atom and the terminal substituent on their neutral and oxidized states. For the latter, the spin density found on the carbon chain is a source of instability; e.g., for R = Au(PPh3), the oxidized compounds are much more accessible electrochemically than the rest of the series but are susceptible to radical attack. Of particular interest is the use of joint experimental and theoretical EPR studies, which allow elucidation of the differences of behavior within the two series. It reveals that the atomic spin density on the metal is not a sufficient criterion to evaluate EPR anisotropy but that the specific nodal properties of the frontier spin-orbitals highly influence the EPR components. The localization of the spin density on specific carbon atoms of the conjugated chain (even numbered) opens up the possibility of building extended systems by targeted radical reactions.

  DOI：

  10.1021/om300584u