Ru(C2C2-ferrocenyl)(1,2-bis(diphenylphosphino)ethane)Cp | 766521-45-3

• 英文名称: Ru(C2C2-ferrocenyl)(1,2-bis(diphenylphosphino)ethane)Cp
• CAS: 766521-45-3
• 化学式: C₄₅H₃₈FeP₂Ru
• 分子量: 797.661
• InChiKey: GBZCCPSRVKGHSX-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：

  Ru(C2C2-ferrocenyl)(1,2-bis(diphenylphosphino)ethane)Cp 在 ferrocenium hexafluorophosphate 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 生成 、
  参考文献：
  名称：

  Oxidative Dimerization of Aryldiynyl–Ruthenium Complexes

  摘要：

  Chemical oxidation of Ru(C CC CR)(dppe)Cp with [FeCp2]PF6 affords the binuclear cations [{Ru(dppe)Cp}(2)C8R2](2+)(PF6-)(2) (R = Ph, 7(2+)(PF6-)(2); R = Fc, 8(2+)(PF6-)(2)) by radical coupling at electron-rich sites involving the inner and outer C C triple bonds, to give cyclobutenediylidene derivatives. In each case, mixtures of symmetrical and asymmetrical isomers were obtained (2:1 for 7(2+)(PF6-)(2), 1:1 for 8(2+)(PF6-)(2)), shown by single-crystal X-ray diffraction structure determinations of 7(2+)-asym(PF6-)(2) and 8(2+)-sym(AsF6-)(2). 8(2+)-sym consists of a central C-4 ring with two =C=C=Ru(dppe)Cp groups in the 1,2-positions and two Fc substituents in the 3,4-positions, whereas for 7(2+)-asym the substituent =Ru(dppe)Cp is in the 1-position, =C=C=Ru(dppe)Cp is in the 2-position, Ph is in the 3-position, and -C CPh is in the 4-position. DFT calculations reveal that the precursor cationic diynyl complexes show important electron density on C-beta and C-delta, suggesting that radical coupling (C-delta + C-delta) or (C-beta + C delta) affords the sym and asym isomers, respectively.

  DOI：

  10.1021/om3005146
• 作为产物：
  描述：

  chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II) 、 ((trimethylsilyl)buta-1,3-diynyl)ferrocene 在 potassium fluoride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以32%的产率得到Ru(C2C2-ferrocenyl)(1,2-bis(diphenylphosphino)ethane)Cp
  参考文献：
  名称：

  Oxidative Dimerization of Aryldiynyl–Ruthenium Complexes

  摘要：

  Chemical oxidation of Ru(C CC CR)(dppe)Cp with [FeCp2]PF6 affords the binuclear cations [{Ru(dppe)Cp}(2)C8R2](2+)(PF6-)(2) (R = Ph, 7(2+)(PF6-)(2); R = Fc, 8(2+)(PF6-)(2)) by radical coupling at electron-rich sites involving the inner and outer C C triple bonds, to give cyclobutenediylidene derivatives. In each case, mixtures of symmetrical and asymmetrical isomers were obtained (2:1 for 7(2+)(PF6-)(2), 1:1 for 8(2+)(PF6-)(2)), shown by single-crystal X-ray diffraction structure determinations of 7(2+)-asym(PF6-)(2) and 8(2+)-sym(AsF6-)(2). 8(2+)-sym consists of a central C-4 ring with two =C=C=Ru(dppe)Cp groups in the 1,2-positions and two Fc substituents in the 3,4-positions, whereas for 7(2+)-asym the substituent =Ru(dppe)Cp is in the 1-position, =C=C=Ru(dppe)Cp is in the 2-position, Ph is in the 3-position, and -C CPh is in the 4-position. DFT calculations reveal that the precursor cationic diynyl complexes show important electron density on C-beta and C-delta, suggesting that radical coupling (C-delta + C-delta) or (C-beta + C delta) affords the sym and asym isomers, respectively.

  DOI：

  10.1021/om3005146

文献信息

• Synthesis, structures and some reactions of Ru(CCCCFc)(PP)Cp (PP=dppm, dppe) and related compounds
  作者：Michael I. Bruce、Frédéric de Montigny、Martyn Jevric、Claude Lapinte、Brian W. Skelton、Mark E. Smith、Allan H. White

  DOI：10.1016/j.jorganchem.2004.05.028

  日期：2004.9

  reacts to give two isomeric complexes 6 and 7, in which the cyano-olefin has added to either CC triple bond. The reaction of RuCl(dppe)Cp with HCCCCFc, carried out in a thf/NEt3 mixture in the presence of Na[BPh4], gave [RuCCC(NEt3)CHFc}(dppe)Cp]BPh4 (8), probably formed by addition of the amine to an (unobserved) intermediate butatrienylidene [Ru(CCCCHFc)(dppe)Cp]+. The reaction of I2 with 8 proceeds via

  Ru（CCCCFc）（PP）Cp [PP = DPPE（1），DPPM（2）]，是在KF（1）或HCCCCFc和K存在下，由RuCl（PP）Cp与FcCCCCSiMe 3之间的反应获得的。[PF 6 ]（2），都添加了dbu。的DPPE复杂发生反应的Co 2（CO）6（L 2）[L 2  =（CO）2，DPPM]，得到3，4其中Co 2（CO）4（L 2）基团连接到所述外CC三键。3（的PPh 3类似物5）也已被表征。相反，四氰基乙烯反应生成两个异构体配合物6和7，其中氰基烯烃已添加至任一CC三键。在Na [BPh 4 ]存在下于thf / NEt 3混合物中进行RuCl（DPPE）Cp与HCCCCFc的反应，得到[Ru CCC（NEt 3）CHFc}（DPPE）Cp] BPh 4（8），可能是通过将胺加到（未观察到的）中间体丁三烯[Ru（CCCCHFc）（DPPE）Cp] +中形成的。