[Ru(tpy)(bpy)H]PF₆ | 156030-72-7

• 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: [Ru(tpy)(bpy)H]PF₆
• 英文别名: [Ru(2,2′:6′,2″-terpyridine)(2,2′-bipyridine)H]PF₆；2,6-dipyridin-2-ylpyridine;2-pyridin-2-ylpyridine;ruthenium(1+) monohydride;hexafluorophosphate
• CAS: 156030-72-7
• 化学式: C₂₅H₂₀N₅Ru*F₆P
• 分子量: 636.501
• InChiKey: FRLMUKYXBSJBPS-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(tpy)(bpy)H]PF₆ 以60%的产率得到氢气
  参考文献：
  名称：

  Rapid Transfer of Hydride Ion from a Ruthenium Complex to C₁ Species in Water

  摘要：

  Solvent water (Gutmann acceptor number, AN = 55) accelerates the rate of reaction of Ru(terpy)(bpy)H+ with CO2 by more than 4 orders of magnitude compared to acetonitrile (AN 18.9) (as reported in Inorg. Chim. Acta 2000, 299, 155). Water also promotes the related reductions of carbon monoxide to formaldehyde and of formaldehyde to methanol by the ruthenium(II) hydride complex.

  DOI：

  10.1021/ja074158w
• 作为产物：
  描述：

  [Ru(2,2':6',2''-terpyridine)(2,2'-bipyridine)(pyridine)](PF6)2 、 三乙胺 以 dimethylformamide 为溶剂， 生成 [Ru(tpy)(bpy)H]PF₆
  参考文献：
  名称：

  Quantitative Photochemical Formation of [Ru(tpy)(bpy)H]⁺

  摘要：

  Quantitative photochemical production of [Ru(tpy)(bpy)H](+) (Ru-H+) was achieved by irradiation of [Ru(tpy)(bpy)(DMF)](2+) (Ru-DMF2+; DMF = N,N-dimethylformamide) in a tetrahydrofuran (THF) solution containing excess triethylamine (NEW. The mechanism of the Ru-H+ formation was investigated in detail. A photochemical ligand substitution reaction of Ru-DMF2+ in THF proceeded to give [Ru(tpy)(bpy)(THF)](2+) (Ru-THF2+) with a quantum yield of (7.6 +/- 0.7) x 10(-2). In the presence of NEt3, a similar photochemical ligand substitution reaction also proceeded quickly, but the products were an equilibrium mixture of Ru-THF2+ and [Ru(tpy)(bpy)(NEt3)](2+) (Ru-NEt32+) with a considerable amount of Ru-H+ even in the first stage of the photochemical reaction. The equilibrium constant between Ru-THF2+ and Ru-NEt32+ was determined as 6.9 +/- 2.1. Irradiation to Ru-NEt32+ gave Ru-H+ with a quantum yield of (9.1 +/- 0.5) x 10(-3). An important intermediate, Ru-NEt32+, was isolated, and its properties were investigated in detail.

  DOI：

  10.1021/ic901080r
• 作为试剂：
  描述：

  1-benzyl-N,N-diethylnicotinamidium cation 在 哌啶 、 [Ru(tpy)(bpy)H]PF₆ 、 BAcPy(+)*PF₆^(1-) 作用下， 以 乙腈 为溶剂， 反应 1.0h， 以100%的产率得到1-benzyl-N,N-diethyl-1,4-dihydronicotinamide
  参考文献：
  名称：

  在碱存在下，由NAD（P）H模型化合物协调的过渡金属配合物及其增强的氢化物给体能力。

  摘要：

  含有NAD（P）H模型化合物，1-苄基-1,4-二氢烟酰胺（BNAH）作为配体[Ru（tpy）（bpy）（BNAH）] 2的钌（II）和rh（I）配合物+（1 a）和[Re（bpy）（CO）3（BNAH）] +（1 b）通过相应的金属氢化物络合物与BNA（+）（1-苄基烟酰胺阳离子）的反应定量生成。在存在pK（a）= 8.9的碱的情况下，1a和1b的还原能力比“游离” BNAH大得多。与不存在Ag / AgNO（3）相比，在不存在和存在三乙胺的条件下，1 a的氧化电位分别为0.55 V和-0.04 V，而“游离” BNAH的氧化电位为0.30V。光谱结果清楚地表明，该碱从1a和1b上的氨基甲酰基基团中提取了一个质子，从而得到了与过渡金属配合物[Ru（tpy）（bpy）（BNAH-H +）] +（3 a ）和[Re（bpy）（CO）3（BNAH-H +）]（3 b）; 这种去质子化是还原能力

  DOI：

  10.1002/chem.200401211

文献信息

• 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
• Understanding the Individual and Combined Effects of Solvent and Lewis Acid on CO₂ Insertion into a Metal Hydride
  作者：Jessica E. Heimann、Wesley H. Bernskoetter、Nilay Hazari

  DOI：10.1021/jacs.9b05192

  日期：2019.7.3

  demonstrate that there is a significant solvent effect on CO2 insertion in the absence of a LA. Although the AN of the solvent has been previously used to predict the rate of CO2 insertion, this work shows that the best model for the rate of insertion is based on the Dimroth-Reichardt ET(30) value of the solvent, a parameter that better accounts for specific solute/solvent interactions.

  CO2 插入金属氢化物键以形成金属甲酸盐是许多 转化催化循环中的关键基本步骤。同样，微观逆反应，即金属甲酸盐脱羧形成金属氢化物和 ，在有机合成和使用有机液体的储氢策略中都很重要。然而，很少有实验研究探索这些反应的机制并确定特定变量（如路易斯酸 (LA) 添加剂或溶剂）的影响，这些变量已被证明会显着影响催化性能。在本研究中，我们使用快速混合停流仪器来研究 插入阳离子氢化钌 [Ru(tpy)bpy)H]PF6 (tpy = 2,2':6',2"-三联吡啶) 的动力学, bpy = 2,2'-联吡啶）在各种溶剂中，LA 存在和不存在的情况下。我们表明，LAs 可以增加该反应的观察速率，并确定在阳离子 LAs 存在下观察到的 插入速率增强的第一个定量趋势，Li+ ≫ Na+ > K+ > Rb+。此外，我们表明使用 LA 观察到的速率增强是依赖于溶剂的。具体而言，随着
• Mechanistic Insight from Activation Parameters for the Reaction of a Ruthenium Hydride Complex with CO₂ in Conventional Solvents and an Ionic Liquid
  作者：Simon Kern、Rudi van Eldik

  DOI：10.1021/ic300718v

  日期：2012.7.2

  performed on the reaction of [RuII(terpy)(bpy)H]+ (terpy = 2,2′,6′,2″-terpyridine; bpy = 2,2′-bipyridine) with CO2 in conventional solvents (water, methanol, and ethanol) and in the ionic liquid [emim][NTf2] ([emim] = 1-ethyl-3-methyl-imidazolium; [NTf2] = bistrifluoromethylsulfonylamide). Second-order rate constants and activation parameters (ΔH⧧, ΔS⧧, and ΔV⧧) were determined for the reaction in all solvents

  对[Ru II（terpy）（bpy）H] +（terpy = 2,2'，6'，2''-联吡啶; bpy = 2,2'-联吡啶）与CO 2在二氯甲烷中的反应进行了详细的动力学研究。常规溶剂（水，甲醇和乙醇）和离子液体中[emim] [NTf 2 ]（[emim] = 1-乙基-3-甲基咪唑鎓； [NTf 2 ] =双三氟甲基磺酰胺）。二级速率常数和激活参数（Δ ħ ⧧，Δ小号⧧，Δ V ⧧确定在所有溶剂中的反应量。二级速率常数与溶剂的受体数相关，而活化参数则支持反应的缔合性质。水中的结果，特别是活化熵（+14±2 JK –1 mol –1）和活化体积（-5.9±0.6 cm 3 mol –1），与其他溶剂的结果明显不同。
• Formation of Novel 1:1 Adducts Accompanied by Regioselective Hydride Transfer from Transition-Metal Hydrido Complexes to NAD(P) Models
  作者：Atsuo Kobayashi、Ryosuke Takatori、Itsumi Kikuchi、Hideo Konno、Kazuhiko Sakamoto、Osamu Ishitani

  DOI：10.1021/om010362v

  日期：2001.8.1

  Important intermediates in regioselective hydride reduction of NAD(P) model compounds were detected by various spectroscopic methods. The metal hydrido complexes [Ru(tpy)(bpy)H](+) and [Re(bpy)-(CO)(3)H] react with the NAD(P) models to give 1:1 adducts, which are cleaved to the 1,4-dihydro form of the models and the solvento complexes, quantitatively.