(η6-C6Me6)ruthenium(II)(aqua)(2,2'-bipyridine)(SO4) | 444177-95-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (η6-C6Me6)ruthenium(II)(aqua)(2,2'-bipyridine)(SO4)
• 英文别名: [(η6-C6Me6)Ru(II)(2,2'-bipyridine)(H2O)](SO4)；[(η6-C6Me6)Ru(2,2'-bipyridine)(H2O)]SO4；[Ru(η6-C6Me6)(2,2'-bipyridine)(H2O)]SO4；[(η6-C6Me6)Ru(II)(bpy)(H2O)](SO4)；1,2,3,4,5,6-Hexamethylbenzene;2-pyridin-2-ylpyridine;ruthenium(2+);sulfate;hydrate
• CAS: 444177-95-1
• 化学式: C₂₂H₂₈N₂ORu*O₄S
• 分子量: 533.611
• InChiKey: CCQWUMIRPHLBIO-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.52
• 重原子数：
  31
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  115
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  sodium hexaflorophosphate 、 (η6-C6Me6)ruthenium(II)(aqua)(2,2'-bipyridine)(SO4) 在 HCOONa 、 NaOH 作用下， 以 水 为溶剂， 以65%的产率得到[(η6-C6Me6)Ru(II)(2,2'-bipyridine)H](PF6)
  参考文献：
  名称：

  pH-Dependent Transfer Hydrogenation of Ketones with HCOONa as a Hydrogen Donor Promoted by (η⁶-C₆Me₆)Ru Complexes

  摘要：

  The paper reports on the development of a new class of water-soluble organometallic catalysts for pH-dependent transfer hydrogenation. An organometallic aqua complex [(eta(6)-C6Me6)Ru-II(bpy)(H2O)](2+) (1, bpy = 2,2'-bipyridine) acts as a catalyst precursor for pH-dependent transfer hydrogenation of water-soluble and -insoluble ketones with HCOONa as a hydrogen donor in water and in biphasic media. Irrespective of the solubility of the ketones toward water, the rate of the transfer hydrogenation shows a sharp maximum around pH 4.0 (in the case of biphasic media, the pH value of the aqueous phase is adopted). In the absence of the reducible ketones, as a function of pH, complex 1 reacts with HCOONa to provide a formato complex [(eta(6)-C6Me6)Ru-II(bpy)(HCOO)](+) (2) as an intermediate of beta-hydrogen elimination and a hydrido complex [(eta(6)-C6Me6)Ru-II(bpy)H](+) (3) as the catalyst for the transfer hydrogenation. The structures of 1(PF6)(2), 2(HCOO).HCOOH, and [(eta(6)-C6Me6)Ru-II(H2O)(3)]SO4.3H(2)O {4(SO4).3H(2)O}, the starting material for the synthesis of 1, were unequivocally determined by X-ray analysis.

  DOI：

  10.1021/om011059x
• 作为产物：
  描述：

  2,2'-联吡啶 、 [(η6-C6Me6)Ru(H2O)3](SO4)*3H2O 以 水 为溶剂， 以90%的产率得到(η6-C6Me6)ruthenium(II)(aqua)(2,2'-bipyridine)(SO4)
  参考文献：
  名称：

  pH-Dependent Transfer Hydrogenation of Ketones with HCOONa as a Hydrogen Donor Promoted by (η⁶-C₆Me₆)Ru Complexes

  摘要：

  The paper reports on the development of a new class of water-soluble organometallic catalysts for pH-dependent transfer hydrogenation. An organometallic aqua complex [(eta(6)-C6Me6)Ru-II(bpy)(H2O)](2+) (1, bpy = 2,2'-bipyridine) acts as a catalyst precursor for pH-dependent transfer hydrogenation of water-soluble and -insoluble ketones with HCOONa as a hydrogen donor in water and in biphasic media. Irrespective of the solubility of the ketones toward water, the rate of the transfer hydrogenation shows a sharp maximum around pH 4.0 (in the case of biphasic media, the pH value of the aqueous phase is adopted). In the absence of the reducible ketones, as a function of pH, complex 1 reacts with HCOONa to provide a formato complex [(eta(6)-C6Me6)Ru-II(bpy)(HCOO)](+) (2) as an intermediate of beta-hydrogen elimination and a hydrido complex [(eta(6)-C6Me6)Ru-II(bpy)H](+) (3) as the catalyst for the transfer hydrogenation. The structures of 1(PF6)(2), 2(HCOO).HCOOH, and [(eta(6)-C6Me6)Ru-II(H2O)(3)]SO4.3H(2)O {4(SO4).3H(2)O}, the starting material for the synthesis of 1, were unequivocally determined by X-ray analysis.

  DOI：

  10.1021/om011059x
• 作为试剂：
  描述：

  二氧化碳 、 氢气 在 (η6-C6Me6)ruthenium(II)(aqua)(2,2'-bipyridine)(SO4) 作用下， 以 水 为溶剂， 生成 甲酸
  参考文献：
  名称：

  水溶性钌水合络合物在酸性条件下催化的二氧化碳水合加氢反应。

  摘要：

  通过使用水溶性钌基水催化剂[（eta6-C6Me6），在酸性条件下（pH 2.5-5.0）在水中将二氧化碳（P（H2 / CO2）= 5.5 / 2.5 MPa）加氢成甲酸（HCOOH） ）RuII（L）（OH2）] SO4（L = 2,2'-联吡啶或4,4'-二甲氧基-2,2'联吡啶）。

  DOI：

  10.1039/b411633j

文献信息

• Aqueous Polymerization of Styrene Promoted by Water-Soluble Robust Ruthenium Hydride Complexes
  作者：Seiji Ogo、Keiji Uehara、Tsutomu Abura、Yoshihito Watanabe、Shunichi Fukuzumi

  DOI：10.1021/om034335b

  日期：2004.6.1

  Aqueous polymerization of styrene in biphasic media (styrene/water) has been achieved by water-soluble robust mononuclear hydride complexes [(η6-C6Me6)RuII(bpy)H]n(X) [1]n(X), where X = SO4 (n = 2) or CF3SO3 (n = 1), bpy = 2,2‘-bipyridine}. The hydride complex [1]2(SO4) was synthesized from the reaction of an aqua complex [(η6-C6Me6)RuII(bpy)(H2O)](SO4) 2(SO4)} with a water-soluble hydrogen donor

  在两相介质（苯乙烯/水）苯乙烯的水性聚合已经由水溶性健壮单核氢化物络合物实现[（η 6 -C 6我6）的Ru II（BPY）H] Ñ（X）[ 1 ] Ñ（ X），其中X = SO 4（n = 2）或CF 3 SO 3（n = 1），bpy = 2,2'-联吡啶}。氢化物配合物[ 1 ] 2（SO 4）是从一个水性络合物[（η的反应合成6 -C 6我6）的Ru II（BPY）（H2 O）]（SO 4） 2（SO 4）}与H 2 O中的水溶性氢供体HCOONa在70-100°C的pH范围为4-12之间。通过X射线分析，1 H和2 H NMR，IR和电喷雾电离质谱（ESI-MS）确定[ 1 ] 2（SO 4）和1（CF 3 SO 3）的结构。X射线分析显示，复杂1（CF 3 SO 3）采用扭曲的八面体与钌原子几何由一个η协调6 -C 6我6个配体，1个双齿bpy配体和1个占据键位置的末端氢配体。络合物[
• Hydride Ion Transfer from Ruthenium(II) Complexes in Water: Kinetics and Mechanism
  作者：Carol Creutz、Mei H. Chou、Hua Hou、James T. Muckerman

  DOI：10.1021/ic101124q

  日期：2010.11.1

  and H3CO− in water are estimated as +1.48, −0.76, and +1.57 eV/molecule (+34, −17.5, +36 kcal/mol), respectively. Theoretical studies of the reactions with CO2 reveal a “product-like” transition state with short C−H and long M−H distances. (Reactant) Ru−H stretched 0.68 Å; (product) C−H stretched only 0.04 Å. The role of water solvent was explored by including one, two, or three water molecules in

  钌（II）与氢化受体的氢化物络合物的反应已经检查的Ru（三联吡啶）（联吡啶）H +，钌（三联吡啶）（DMB）H +，和Ru（η 6 -C 6我6）（联吡啶） （H）+在25°C的水性介质中（叔比= 2,2'; 6'，2'-吡啶，bpy = 2,2'-联吡啶，DMB = 4,4'-二甲基-2,2' -联吡啶）。受体包括CO 2，CO，CH 2 O和H 3 O +。与钌发生反应CO（三联吡啶）（DMB）H +为1.2（0.2）的速率常数×10 1中号-1小号-1，但是对于钌（η 6 -C 6我6）（联吡啶）（H）+，反应非常慢，ķ ≤的0.1M -1小号-1。的Ru（三联吡啶）（联吡啶）H +和Ru（η 6 -C 6我6）（联吡啶）（H）+用CH反应2 ö与（6±4）×10速率常数6和1.1×10 3中号-1 s -1。钌的反应（η 6 -C 6我6）（联吡啶）（H）+用酸展品直接的，第二级动力学，与速率成比例的[Ru（η
• Accelerating Effect of a Proton on the Reduction of CO₂ Dissolved in Water under Acidic Conditions. Isolation, Crystal Structure, and Reducing Ability of a Water-Soluble Ruthenium Hydride Complex
  作者：Hideki Hayashi、Seiji Ogo、Tsutomu Abura、Shunichi Fukuzumi

  DOI：10.1021/ja036117f

  日期：2003.11.1

  A water-soluble hydride complex [(eta6-C6Me6)RuII(bpy)H]+ 1, bpy = 2,2'-bipyridine} serves as a robust reducing agent for the reduction of CO2 in water in a pH range of about 3-5 at ambient temperature under stoichiometric conditions. The structure of 1 was unequivocally determined by X-ray analysis. The mechanism of acid-catalyzed reduction of CO2 promoted by 1 in water under acidic conditions is disclosed.