[(3-MeC5H3N-2-C6H4)Ru(μ-I)(CO)2]2 | 185553-67-7

• 英文名称: [(3-MeC5H3N-2-C6H4)Ru(μ-I)(CO)2]2
• CAS: 185553-67-7
• 化学式: C₂₈H₂₀I₂N₂O₄Ru₂
• 分子量: 904.427
• InChiKey: RYCJVYFXBGOQRJ-UHFFFAOYSA-L

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：

  4-甲基吡啶 、 [(3-MeC5H3N-2-C6H4)Ru(μ-I)(CO)2]2 、 丁炔二酸二甲酯 以 二氯甲烷 、 氯苯 为溶剂， 生成 [(3-MeC5H3N-2-C6H4(MeO2CC=CCO2Me))RuI(CO)2(4-MePy)]
  参考文献：
  名称：

  Mechanism of Alkyne Insertion into the Ru−C Bonds of Orthoruthenated Compounds Featuring Similarity of the Ru(II) and Pd(II) Reactions

  摘要：

  The pseudo-first-order rate constants k(obs) for the reaction between the ring-substituted orthoruthenated N,N-dimethylbenzylamines [Ru-II(eta(G)-C6H6)(o-C(6)H(3)RCH(2)NMe(2))Cl] (R = 4,5-(MeO)(2), 5-Me, H, 5-F), and alkynes R'C drop CR'' (R'/R'' = Ph/Ph, Ph/C6H4CF3-3, Ph/C6H4NO2-4, Et/Et, CO(2)Me/CO(2)Me) to afford the isoquinolinium cations coordinated to the [Ru-0(eta(6)-C6H6)] moiety are a linear function of [R'C drop CR''] in methanol at 20.0-40.0 degrees C in accord with the rate-determining insertion of alkyne into the Ru-C bond. The latter was confirmed by the observation that the electron-donating groups R at the dimethylbenzylamine ruthenocycle favor the insertion and the slope of the corresponding Hammett plot equals -1.6 against sigma(+). The electron-poor alkynes react slower than the electron-rich ones. An X-ray structural investigation of the product of the MeO(2)CC drop CCO(2)Me reaction with the related ruthenocycle [(3-MeC(5)H(3)N-2-C6H4)Ru(mu-I)(CO)(2)](2) demonstrates that the alkyne inserts into the Ru-C bond. Addition of LiCl retards the insertion markedly indicative of the importance of the ionization of the coordinated chloride. The major reaction pathway involves the solvento species [Ru-II(eta(6)-C6H6)(o-C(6)H(3)RCH(2)NMe(2))(MeOH)](+), the existence of which was confirmed by the spectrophotometric study of the starting compound in the presence of LiCl. All the observations reported show that the d(6) system under study is very mechanistically similar to the insertion, of alkynes into the dinuclear d(8) Pd-II complexes [Pd(o-C(6)H(3)RCH(2)NMe(2))mu-Cl)](2), the key difference being the ways of creation of a coordinative site readily accessible by alkyne. These are the ionization of the Ru-CI bond and the cleavage of the [Pd(mu-Cl)(2)Pd] bridge in the ruthenium and palladium cases, respectively.

  DOI：

  10.1021/om960674b
• 作为产物：
  描述：

  [(3-MeC5H3N-2-C6H4)Ru(μ-Cl)(CO)2]2 、 sodium iodide 以 丙酮 为溶剂， 以92%的产率得到[(3-MeC5H3N-2-C6H4)Ru(μ-I)(CO)2]2
  参考文献：
  名称：

  Mechanism of Alkyne Insertion into the Ru−C Bonds of Orthoruthenated Compounds Featuring Similarity of the Ru(II) and Pd(II) Reactions

  摘要：

  The pseudo-first-order rate constants k(obs) for the reaction between the ring-substituted orthoruthenated N,N-dimethylbenzylamines [Ru-II(eta(G)-C6H6)(o-C(6)H(3)RCH(2)NMe(2))Cl] (R = 4,5-(MeO)(2), 5-Me, H, 5-F), and alkynes R'C drop CR'' (R'/R'' = Ph/Ph, Ph/C6H4CF3-3, Ph/C6H4NO2-4, Et/Et, CO(2)Me/CO(2)Me) to afford the isoquinolinium cations coordinated to the [Ru-0(eta(6)-C6H6)] moiety are a linear function of [R'C drop CR''] in methanol at 20.0-40.0 degrees C in accord with the rate-determining insertion of alkyne into the Ru-C bond. The latter was confirmed by the observation that the electron-donating groups R at the dimethylbenzylamine ruthenocycle favor the insertion and the slope of the corresponding Hammett plot equals -1.6 against sigma(+). The electron-poor alkynes react slower than the electron-rich ones. An X-ray structural investigation of the product of the MeO(2)CC drop CCO(2)Me reaction with the related ruthenocycle [(3-MeC(5)H(3)N-2-C6H4)Ru(mu-I)(CO)(2)](2) demonstrates that the alkyne inserts into the Ru-C bond. Addition of LiCl retards the insertion markedly indicative of the importance of the ionization of the coordinated chloride. The major reaction pathway involves the solvento species [Ru-II(eta(6)-C6H6)(o-C(6)H(3)RCH(2)NMe(2))(MeOH)](+), the existence of which was confirmed by the spectrophotometric study of the starting compound in the presence of LiCl. All the observations reported show that the d(6) system under study is very mechanistically similar to the insertion, of alkynes into the dinuclear d(8) Pd-II complexes [Pd(o-C(6)H(3)RCH(2)NMe(2))mu-Cl)](2), the key difference being the ways of creation of a coordinative site readily accessible by alkyne. These are the ionization of the Ru-CI bond and the cleavage of the [Pd(mu-Cl)(2)Pd] bridge in the ruthenium and palladium cases, respectively.

  DOI：

  10.1021/om960674b