[(η⁵-C₅H₄)₂(SiMe₂)]Ru₂(CO)₄Me₂ | 240818-18-2

• 英文名称: [(η⁵-C₅H₄)₂(SiMe₂)]Ru₂(CO)₄Me₂
• 英文别名: [Ru2(μ-(η(5)-C5H4)2SiMe2)(CH3)2(CO)4]
• CAS: 240818-18-2
• 化学式: C₁₈H₂₀O₄Ru₂Si
• 分子量: 530.58
• InChiKey: RCCWKEVOLMFAGO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [(η⁵-C₅H₄)₂(SiMe₂)]Ru₂(CO)₄Me₂ 以 苯 为溶剂， 反应 0.5h， 以43%的产率得到
  参考文献：
  名称：

  Intramolecular C–H Bond Activation in Bridged Dicyclopentadienyl Dimethyl Dinuclear Complexes

  摘要：

  Photolysis of the doubly bridged dicyclopentadienyl dimethyl dinuclear complexes [(eta(5)-C5H2R)(2)(SiMe2)(2)]-M-2(CO)(4)Me-2 (M = Ru, R = H (2a), Bu-t (2b); M = Fe, R = H (2c)) in benzene yields the corresponding methylene-bridged complexes [(eta(5)-C5H2R)(2)(SiMe2)(2)]M-2(CO)(2)(mu-CO)(mu-CH2) (3a-c) and the M-M-bonded complexes [(eta(5)-C5H2R)(2)(SiMe2)(2)]M-2(CO)(4) (1a-c). Irradiation of the analogous diethyl complex [(eta(5)-C5H2R)(2)(SiMe2)(2)]Ru-2(CO)(4)Et-2 (4) affords only 1a. Unlike the case for the doubly bridged complexes, photolysis of the singly bridged dicyclopentadienyl dimethyl diruthenium complexes [(eta(5)-C5H4)(2)(EMe2)]Ru-2(CO)(4)Me-2 (E = C (5a); E = Si (5b)) in benzene yields the corresponding "twisted" ruthenium methyl complexes with a cyclopentadienyl Ru sigma bond (eta(5),eta(5):eta(1)-C5H4(EMe2)C5H3)[Ru(CO)(2)][Ru(CO)(2)Me] (6a,b) and the similar phenyl complexes (eta(5),eta(5):eta(1)-C5H4(EMe2)C5H3)[Ru(CO)(2)][Ru(CO)(2)Ph] (7a,b), from reaction with the benzene solvent. Plausible mechanisms for the formation of the different types of products are proposed involving intramolecular C H bond activation. The molecular structures of 2a,c, 3a,c, 4, 5a, 6a, and 7h, determined by X-ray diffraction, are also presented.

  DOI：

  10.1021/om400986a
• 作为产物：
  描述：

  [(η5-C5H4)2(SiMe2)]Ru2(CO)4 、 碘甲烷 在 sodium amalgam 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以59%的产率得到[(η⁵-C₅H₄)₂(SiMe₂)]Ru₂(CO)₄Me₂
  参考文献：
  名称：

  Intramolecular C–H Bond Activation in Bridged Dicyclopentadienyl Dimethyl Dinuclear Complexes

  摘要：

  Photolysis of the doubly bridged dicyclopentadienyl dimethyl dinuclear complexes [(eta(5)-C5H2R)(2)(SiMe2)(2)]-M-2(CO)(4)Me-2 (M = Ru, R = H (2a), Bu-t (2b); M = Fe, R = H (2c)) in benzene yields the corresponding methylene-bridged complexes [(eta(5)-C5H2R)(2)(SiMe2)(2)]M-2(CO)(2)(mu-CO)(mu-CH2) (3a-c) and the M-M-bonded complexes [(eta(5)-C5H2R)(2)(SiMe2)(2)]M-2(CO)(4) (1a-c). Irradiation of the analogous diethyl complex [(eta(5)-C5H2R)(2)(SiMe2)(2)]Ru-2(CO)(4)Et-2 (4) affords only 1a. Unlike the case for the doubly bridged complexes, photolysis of the singly bridged dicyclopentadienyl dimethyl diruthenium complexes [(eta(5)-C5H4)(2)(EMe2)]Ru-2(CO)(4)Me-2 (E = C (5a); E = Si (5b)) in benzene yields the corresponding "twisted" ruthenium methyl complexes with a cyclopentadienyl Ru sigma bond (eta(5),eta(5):eta(1)-C5H4(EMe2)C5H3)[Ru(CO)(2)][Ru(CO)(2)Me] (6a,b) and the similar phenyl complexes (eta(5),eta(5):eta(1)-C5H4(EMe2)C5H3)[Ru(CO)(2)][Ru(CO)(2)Ph] (7a,b), from reaction with the benzene solvent. Plausible mechanisms for the formation of the different types of products are proposed involving intramolecular C H bond activation. The molecular structures of 2a,c, 3a,c, 4, 5a, 6a, and 7h, determined by X-ray diffraction, are also presented.

  DOI：

  10.1021/om400986a

文献信息

• Me₂Si(η⁵-C₅H₄)₂-Bridged Dinuclear Ruthenium Complexes:  X-ray Crystal Structures of [Ru₂{μ-(η⁵-C₅H₄)₂SiMe₂}(Cl)₂(CO)₄] and [Ru₂{μ-(η⁵-C₅H₄)₂SiMe₂}(μ-Br)(CO)₄][BF₄]
  作者：Richard Fröhlich、José Gimeno、Mercedes González-Cueva、Elena Lastra、Javier Borge、Santiago García-Granda

  DOI：10.1021/om980547a

  日期：1999.8.1

  molecule. Irradiation of a solution of 4c and PCy3 in THF leads to carbonyl substitutions to yield the monocarbonyl complex [Ru2μ-(η5-C5H4)2SiMe2}(I)2(CO)2(PCy3)2] (6c). Analogous isocyanide carbonyl substituted complexes [Ru2μ-(η5-C5H4)2SiMe2}(I)2(CNR)x(CO)4-x] (R = CH2Ph, x = 1 (7a), x = 2 (7b), x = 3 (7c), x = 4 (7d); R = Cy, x = 1 (8a), x = 2 (8b), x = 3 (8c), x = 4 (8d)) have been obtained by UV irradiation

  双核四羰治疗复杂的[Ru 2 μ-（η 5 -C 5 H ^ 4）2森达2 }（μ-CO）2（CO）2 ]（1）与HBF 4在二氯甲烷中通向电加成一个质子的，得到桥接氢化物络合物的[Ru 2 μ-（η 5 -C 5 H ^ 4）2森达2 }（μ-H）（CO）4 ] [BF 4 ]（2）。配合物1也与Li反应[BHEt 3]，得到桥接亚甲基复杂的[Ru 2 μ-（η 5 -C 5 H ^ 4）2森达2 }（μ-CH 2）（μ-CO）（CO）2 ]（3）。双核配合物的[Ru 2 μ-（η 5 -C 5 H ^ 4）2森达2 }（X）2（CO）4 ]（X =氯（4A），溴（图4b），和I（图4c））具有从配合物1与N的反应中以高收率合成-CH 2 Cl 2中的-氯代琥珀酰亚胺（X = Cl）和X 2（X = Br，I）。复杂的结构4A已经通过X射线晶体学显示围绕由桥接我连接各钌原子的三条腿的钢琴凳几何被确定2的Si（η