diruthenocenyl ketone | 147041-84-7

• 英文名称: diruthenocenyl ketone
• 英文别名: diruthenocenylketone
• CAS: 147041-84-7
• 化学式: C₂₁H₁₈ORu₂
• 分子量: 488.513
• InChiKey: VIBYAYMIIIAHBD-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：

  diruthenocenyl ketone 、 lithium aluminium tetrahydride 在 三氯化铝 作用下， 以 乙醚 为溶剂， 以82%的产率得到diruthenocenylmethane
  参考文献：
  名称：

  与二烯碳烯基甲烷及其相关化合物中卤素迁移有关的混合价态

  摘要：

  摘要首先以30％的收率通过钌茂茂金属（RcH）与丁基锂（BuLi）和N，N-N-二甲基氨基甲酰氯的一步反应制备作为二茂铁烯基甲烷（RcCH 2 Rc，2）的前体的二茂碳烯酮（RcCORc，1）。 。2与I 2和异二十二碳烯（IV）+ PF 6-（[RcHI] + PF 6-）的反应制得的混合价盐形式为[Ru II Cp（C 5 H 4 CH 2 C 5 H 4）CpRu IV I] + Y-（Y ＝ I 3（3），PF 6（4）），其中观察到与碘在Ru II和Ru IV原子之间迁移有关的分子内电子交换反应。对于丙酮中的3，反应（E a）的活化能估计为31.0±0.6 kJ mol -1，小于混合价[RcRcI] + I 3-盐的相应值（36.5±0.6 kJ mol -1）。2与[RcHCI] + PF 6-或[RcHBr] + PF 6-盐反应得到a，

  DOI：

  10.1016/0020-1693(94)04036-2
• 作为产物：
  描述：

  二茂钌 、 ruthenocene carboxylic acid 在 三氯化铝 、 五氯化磷 、 水 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 以55%的产率得到diruthenocenyl ketone
  参考文献：
  名称：

  Hydride Abstraction Reactivity of Haloruthenoceniums and Haloosmoceniums

  摘要：

  [Cp(2)RuCl]PF6 reacts with benzylruthenocene in acetonitrile with a 1:1 stoichiometry to produce Cp(2)Ru and phenylruthenocenyl methylium cation. Similar hydride abstraction reactivity has also been observed with diruthenocenylmethane, ethylruthenocene, and benzylferrocene. The complexes [Cp(2)MX](+) (M = Ru, Os; X = Cl, Br, I) also react with leuco crystal violet and leuco malachite green to give the corresponding carbenium ions but do not exhibit any detectable reactivity with triphenylmethane, cycloheptatriene, or xanthene. On the basis of these observations, the PHR+ values for the [Cp(2)MX](+) species are estimated to be between +4.7 and +6.9.

  DOI：

  10.1021/om9606247

文献信息

• Competitive NH···Ru/Fe Hydrogen Bonding in Ferrocenyl Ruthenocenyl Tosyl Hydrazone
  作者：Philipp Veit、Ephraim Prantl、Christoph Förster、Katja Heinze

  DOI：10.1021/acs.organomet.5b00963

  日期：2016.1.25

  A strong nonclassical NH center dot center dot center dot Fe intramolecular hydrogen bond (IHB) is present in the literature-known diferrocenyl tosyl hydrazone (1). Here, we confirm by NMR and IR spectroscopy as well as by XRD methods that an analogous NH center dot center dot center dot Ru IHE is present in the heavier homologue diruthenocenyl tosyl hydrazone (2). The NH center dot center dot center dot Ru IHB in 2 is stronger than the NH center dot center dot center dot Fe IHB in 1 by 6 kJ mol(-1), as determined by Eft spectroscopy. Further, we probed the E/Z isomer directing abilities of NH center dot center dot center dot M IHBs in the synthesis of the mixed metallocenyl compound ferrocenyl ruthenocenyl tosyl hydrazone (3). 3 is obtained as a mixture of the Z and E isomers (3a,b) with NH center dot center dot center dot Ru and NH center dot center dot center dot Fe IHBs, respectively. At 111 degrees C, 3a is preferred with an isomeric ratio of 10:1 (91% 3a). The formation of the isomeric mixture allows a direct comparison of the competitive NH center dot center dot center dot Ru/Fe hydrogen bonding. The underlying reason for the 3a:3b ratio is of thermodynamic nature, rooted in the differences in strengths of the NH center dot center dot center dot M IHBs of Fe and Ru. Thermal and photochemical approaches and protonation to the corresponding iminium/carbenium ions [H-3a](+)/[H-3b](+) were employed to overcome the barrier for the E -> Z isomerization 3b -> 3a, with concomitant switching of the NH center dot center dot center dot M IHB.