[Ru(η6-C6Me6)(bpy)H](trifluoromethanesulfonate) | 637740-20-6

• 英文名称: [Ru(η6-C6Me6)(bpy)H](trifluoromethanesulfonate)
• 英文别名: [Ru(η⁶-C₆Me₆)(bpy)H](trifluoromethanesulfonate)；[Ru(hexamethylbenzene)(2,2′-bipyridine)(H)](trifluoromethanesulfonate)；[Ru(η⁶-C₆Me₆)(bpy)H](OTf)；[Ru(HMB)(bpy)(H)](OTf)；[Ru(η6-C6Me6)(2,2'-bipyridine)H](triflate)；[η6-C6Me6)(bipy)Ru(H)](OTf)2
• CAS: 637740-20-6
• 化学式: CF₃O₃S*C₂₂H₂₇N₂Ru
• 分子量: 569.61
• InChiKey: YOTCUNAUCKQUKF-UHFFFAOYSA-M

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(η6-C6Me6)(bpy)H](trifluoromethanesulfonate) 、 水 在 CO 作用下， 以 水 为溶剂， 生成 [(η(6)-hexamethylbenzene)Ru(2,2'-bipyridine)(H2O)](2+)
  参考文献：
  名称：

  水中钌（II）配合物的氢化物离子转移：动力学和机理

  摘要：

  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

  DOI：

  10.1021/ic101124q
• 作为产物：
  描述：

  [η6-C6Me6)(bipy)Ru(H2O)](OTf)2 、 sodium tetrahydroborate 以 甲醇 为溶剂， 生成 [Ru(η6-C6Me6)(bpy)H](trifluoromethanesulfonate)
  参考文献：
  名称：

  Catalytic deoxygenation of terminal-diols under acidic aqueous conditions by the ruthenium complexes [(η6-arene)Ru(X)(N∩N)](OTf)n, X=H2O, H, η6-arene=p-Me-iPr-C6H4, C6Me6, N∩N=bipy, phen, 6,6′-diamino-bipy, 2,9-diamino-phen, n=1, 2)

  摘要：

  A series of ruthenium complexes of the general composition [(eta(6) -arene)(N boolean AND N)Ru(X)] (Y)(n), (arene = p-Me-Pr-i-C6H4, C6Me6; N boolean AND N = bipy, phen, 6,6'-diamino-2,2'-bipyridine, 2,9-diamino-1,10-phenanthroline; X=Cl, H, H2O; Y=Cl, OTf) was synthesized and the new compounds exhaustively structurally characterized by standard techniques (NMR, IR, elemental analysis, single-crystal X-ray crystallography). The single-crystal X-ray structures of [(p-Me-Pr-i-C6H4)Ru(dabipy)Cl][CI] (3CI[CI]), [(p-Me-Pr-i-C6H4)Ru(daphen)CI][CI] (4CI[CI]), [(C6Me6)Ru(dabipy)CI][CI] (7CI[CI]), [(C6Me6)Ru(daphen)CI][CI] (8CI[OTf]), [(p-Me-Pr-i-C6H4)Ru(bipy)(H2O)][OTf](2) (1O[OTf](2)), [(p-Me-Pr-i-C6H4)Ru(dabipy)(H2O)][OTf](2) (3O[OTf](2)), [(p-Me-Pr-i-C6H4)Ru(dabipy)(H2O)][SO4] (3O[SO4]), [(P-Me-(PrC6H4)-Pr-i)-Ru(daphen)(H2O)][OTf](2) (4O[OTf](2)), [(C6Me6)Ru(daphen)(MeOH)][OTf](2) (8(MeOH)[OTf](2)), [(p-Me-Pr-i-C6H4)Ru(dabipy)(H)][OTf] (3H[OTf]), [(p-Me-Pr-i-C6H4)Ru(daphen)(H)][OTf] (4H[OTf]), [(C6Me6)Ru(dabipy-BH2-OTf)(H)] (7H[-NH2-BH2-OTf]) have been determined. Under 750-1100 psi (5-7.5 MPa) of hydrogen pressure at 110 degrees C in the presence of acid and water in sulfolane solvent the aquo complexes form active catalysts for the selective deoxygenation of terminal diols, notably 1,2-hexanediol, to the corresponding primary alcohol, i.e., 1-hexanol in up to 60% yield. The presence of amino functions on the ortho-positions of the chelating ligands results in lower catalyst activity. Under the same reaction conditions the catalysts fail to convert glycerol to GC-detectable products. At the higher temperatures (T> 150 degrees C) possibly required for glycerol activation the catalysts show increasing decomposition with increasing temperature. (C) 2007 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2007.08.008

文献信息

• Proton-Coupled Group Transfer Enables Concerted Protonation Pathways Relevant to Small-Molecule Activation
  作者：Renato N. Sampaio、Brian N. DiMarco、Javier J. Concepcion

  DOI：10.1021/acs.inorgchem.1c01609

  日期：2021.11.15

  is coupled with the transfer of its negatively charged counterpart to carbon dioxide (CO2)─a process termed proton-coupled group transfer─to stoichiometrically produce a metal-hydride complex and a carbonate species. These previously unidentified pathways have played key roles in CO2 and proton reduction catalysis by enabling the generation of key intermediates such as hydrides and metallocarboxylic

  Nature 使用协同反应的机制鉴定，其中所有的键断裂和键形成都发生在一个步骤中，这激发了通过绕过高能中间体的途径进行人工合成转化的合理设计，否则这些中间体在热力学和动力学上是无法进入的。在这一贡献中，我们电化学活化了有机金属钌 (II) 络合物，以表明在乙腈溶液中，来自弱布朗斯台德酸（例如水和甲醇）的质子的运动与其带负电荷的对应物转移到二氧化碳中相结合（ CO 2 )─称为质子耦合基团转移的过程─以化学计量方式产生金属氢化物络合物和碳酸盐物质。这些以前未知的途径通过生成氢化物和金属羧酸等关键中间体在 CO 2和质子还原催化中发挥了关键作用，而它们对碳酸的适用性可能为通过烷基化和羧化反应电合成化学商品提供替代方法.
• 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.