[ruthenium(II)(2,2′:6′,2″-terpyridine)(2,2′-bipyridine)](1+) | 156030-71-6

• 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: [ruthenium(II)(2,2′:6′,2″-terpyridine)(2,2′-bipyridine)](1+)
• 英文别名: [Ru(2,2':6",2"-terpyridine)(2,2′-bipyridine)H]⁺；[Ru(tpy)(bpy)H]⁺；[Ru(tpy)(bpy)](1+)；[Ru(2,2':6',2''-terpyridine)(2,2'-bipyridine)H](1+)；[Ru(2,2';6',2''-terpyridine)(2,2'-bipyridine)H](1+)；Ru(2,2':6',2''-terpyridine)(2,2'-bipyridine)H(1+)
• CAS: 156030-71-6
• 化学式: C₂₅H₂₀N₅Ru
• 分子量: 491.537
• InChiKey: UGTFYRJDRCVBEA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [ruthenium(II)(2,2′:6′,2″-terpyridine)(2,2′-bipyridine)](1+) 、 1-methyl-3-trifluoromethylpyridinium hexafluorophosphate 以 氘代乙腈 为溶剂， 以100%的产率得到[ruthenium(II)(2,2′:6′,2″-terpyridine)(2,2′-bipyridine)(η²-1-methyl-3-trifluoromethyl-1,4-dihydropyridine)](2+)
  参考文献：
  名称：

  η的形成2配位的二氢吡啶钌（II）通过从钌（II）氢化物转移到吡啶鎓阳离子配合物的

  摘要：

  各种吡啶鎓阳离子在3位上带有-CF 3取代基和不带有-CF 3取代基和[Ru（tpy）（bpy）H] +（tpy = 2,2'：6'，2''-叔吡啶和bpy = 2， 2'-联吡啶）进行了详细研究。协调到的Ru（II）络合物在η相应1,4-二氢吡啶2进行定量形成在初始阶段通过一个C = C键模式。观察到的唯一例外是在1-苄基吡啶鎓阳离子的情况下，其中两种加合物与1,4-二氢吡啶和1,2-二氢吡啶的比例为96：4的混合物形成。在所有反应中，Ru-（C═C）键的裂解均以较慢的速率进行，从而得到相应的二氢吡啶和[Ru（tpy）（bpy）（NCCH 3）] 2+当乙腈用作溶剂时。加合物形成的动力学活化参数表明1，4-区域选择性是由空间受限结构的形成诱导的。

  DOI：

  10.1021/om400862n
• 作为产物：
  描述：

  [Ru(2,2':6',2''-terpyridine)(2,2'-bipyridine)(pyridine)](PF6)2 在 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 [ruthenium(II)(2,2′:6′,2″-terpyridine)(2,2′-bipyridine)](1+)
  参考文献：
  名称：

  A novel type of hydride-transfer photocatalysis by Ru^II–pyridine complexes: regiocontrolled reduction of an NAD(P) model compound by triethylamine

  摘要：

  [Ru(trpy)(bpy)(py)]2+（trpy = 2,2â² ：6,2â²,2â³-三吡啶，bpy = 2,2â²-联吡啶，py = 吡啶）和[Ru(LL)2(py)2]2+（LL = 双齿配体）光催化了 1-苄基-4-氨基甲酰基吡啶阳离子以二氢形式的区域控制还原，没有形成半还原二聚体、光催化是通过光取代 Ru 复合物中的 py 配体并随后光转化为 [Ru(trpy)(bpy)H]+ 或 [Ru(LL)2(py)H]+。

  DOI：

  10.1039/c39940000367
• 作为试剂：
  描述：

  1,3-dimethyl-benzoimidazolium 在 [ruthenium(II)(2,2′:6′,2″-terpyridine)(2,2′-bipyridine)](1+) 作用下， 以 氘代乙腈 为溶剂， 生成 1,3-二甲基-2H-苯并咪唑
  参考文献：
  名称：

  氢化钌 (II) 配合物的热力学和动力学氢度

  摘要：

  尽管过渡金属氢化物的氢度（ΔG（H–）°（MH）对于反应 M–H → M+ + H–）在催化和太阳能存储中的一系列重要反应中具有根本重要性，但我们的（J . Am. Chem. Soc. 2009, 131, 2794) 是唯一报告的水溶剂值，并且没有将这些值与已经确定的更广泛范围的乙腈溶剂进行比较的基础，尤其是。因此，我们使用了多种方法来确定先前在水中研究的 Ru(II) 氢化物配合物在乙腈中的氢度值。对于 [Ru(η(6)-C6Me6)(bpy)H]+ (bpy = 2,2'-联吡啶)，我们使用了基于 [Ru(η(6)-C6Me6) 酸度评估的热力学循环(bpy)H]+ pKa = 22.5 ± 0.1 和 [Ru(η(6)-C6Me6)(bpy)(NCCH3)(1/0)](2+/0) 电化学势（-1.22 V vs Fc+/ Fc)。对于 [Ru(tpy)(bpy)H]+ (tpy =

  DOI：

  10.1021/ja302937q

文献信息

• Development of an Efficient and Durable Photocatalytic System for Hydride Reduction of an NAD(P)⁺ Model Compound Using a Ruthenium(II) Complex Based on Mechanistic Studies
  作者：Yasuo Matsubara、Kichitaro Koga、Atsuo Kobayashi、Hideo Konno、Kazuhiko Sakamoto、Tatsuki Morimoto、Osamu Ishitani

  DOI：10.1021/ja1040122

  日期：2010.8.4

  mechanistic study, an efficient and durable photocatalytic system for selective hydride reduction of an NAD(P)(+) model compound has been developed. The photocatalytic reaction is initiated by the formation of [Ru(tpy)(bpy)(NEt(3))](2+) (Ru-NEt(3)(2+)) via the photochemical ligand substitution of Ru-L(2+). For this reason, the production rate of 1,4-BNAH using [Ru(tpy)(bpy)(MeCN)](2+) (Ru-MeCN(2+)) as a photocatalyst

  使用 [Ru(tpy)(bpy)(L)](2+) (Ru) 将 1-苄基烟酰胺阳离子 (BNA(+)) 光催化还原为 1,4-二氢形式 (1,4-BNAH) 的机理-L(2+)，其中 tpy = 2,2':6',2''-三联吡啶，bpy = 2,2'-联吡啶，L = 吡啶和 MeCN) 作为光催化剂，NEt(3) 作为光催化剂还原剂已明确。在此机理研究的基础上，开发了一种高效耐用的光催化系统，用于选择性氢化物还原 NAD(P)(+) 模型化合物。光催化反应是通过形成 [Ru(tpy)(bpy)(NEt(3))](2+) (Ru-NEt(3)(2+)) 通过光化学配体取代 Ru-L( 2+）。为此，使用 [Ru(tpy)(bpy)(MeCN)](2+) (Ru-MeCN(2+)) 作为光催化剂的 1,4-BNAH 的产率，MeCN配体的光消除量子产率大于[Ru(tpy)(bpy)(吡啶)](
• Hydride Reduction of NAD(P)⁺ Model Compounds with a Ru(II)–Hydrido Complex
  作者：Kichitaro Koga、Yasuo Matsubara、Tatsumi Kosaka、Kazuhide Koike、Tatsuki Morimoto、Osamu Ishitani

  DOI：10.1021/acs.organomet.5b00713

  日期：2015.12.14

  In order to better understand the regioselective hydride transfer of metal hydrido complexes to NAD(P)(+) model compounds, reactions of [Ru(tpy)(bpy)H](+) (Ru-H: tpy = 2,2':6 '',2 ''-terpyridine, bpy = 2,2'-bipyridine) with various substituent NAD(P)(+) model compounds were investigated in detail. All of the NAD(P)(+) model compounds accepted hydride from Ru-H, yielding 1:1 adducts, where the dihydro form(s) of the model compounds coordinated with the carbamoyl group to the Ru(II) center of [Ru(tpy)(bpy)](2+), with very different reaction rates. Some reactions produced the adduct with only the 1,4-dihydro structure, whereas others produced a mixture of two adducts, with a 1,4- or 1,2-dihydro structure. In particular, temperature-dependent adduct formation kinetics studies provided important information on the transition state(s) of the hydride transfer reactions and factors for determining the regioselectivity. Most adducts were cleaved to the corresponding free dihydro product(s) with the same distribution of the regioisomers to the adduct(s).
• Synthesis and properties of [Ru(tpy)(4,4′-X2bpy)H]+ (tpy=2,2′:6′,2″-terpyridine, bpy=2,2′-bipyridine, X=H and MeO), and their reactions with CO2
  作者：Hideo Konno、Atsuo Kobayashi、Kazuhiko Sakamoto、Florencia Fagalde、Néstor E. Katz、Hideki Saitoh、Osamu Ishitani

  DOI：10.1016/s0020-1693(99)00488-0

  日期：2000.3

  A novel type of hydride complex [Ru(tpy)(4,4'-X(2)bpy)H](+) (X = H and MeO) was synthesized. The stronger hydridic character of the complexes compared with [Ru(bpy)(2)(L)H](+) type complexes (L = CO, PPh3 and AsPh3) was demonstrated by the relatively high chemical shifts of Ru-H in the H-1 NMR spectra and by higher reactivities with CO2. The reactions of [Ru(tpy)(4,4'-X(2)bpy)H](+) with CO2 occurred at second-order rate constants varying from (4.69 +/- 0.02) to (5.51 +/- 0.04) x 10(-3) M-1 s(-1) depending on both solvent and X, giving the formato complexes [Ru(tpy)(4,4'-X(2)bpy)(OCHO)](+) quantitatively. The rate constant was increased with the increase of solvent acceptor number, and the reaction of [Ru(tpy)4,4'-(MeO)(2)bpy}H](+) with CO2 was found to be 3.6 times faster than that of [Ru(tpy)(bpy)H](+). These results suggest that nucleophilic attack of the hydride ligand to the carbon atom of CO2 is the rate determining step for the formation of the formato complex. The structure of the formato complex [Ru(tpy)(bpy)(OCHO)](PF6) was determined by X-ray crystallographic analysis. (C) 2000 Elsevier Science S.A. All rights reserved.
• Reaction of an NAD(P)+ model compound coordinated to a transition metal complex with ruthenium and rhenium hydrido complexes
  作者：Atsuo Kobayashi、Kazuhiko Sakamoto、Osamu Ishitani

  DOI：10.1016/j.inoche.2005.01.022

  日期：2005.4

  Ruthenium(II) and rhenium(I) complexes with a deprotonated 1-benzylamidium cation as ligand are reduced by metal hydrido complexes. The products are binuclear complexes with a deprotonated 1-benzyl-1,4-dihydronicotinamide (BNAH) ligand, such as [Ru(tpy)(bpy)}(2)(BNAH-H+)](3+). The reducing ability of [Ru(tpy)(bpy)}(2)(BNAH-H+)](3+) is similar to that of free BNAH but less than for the corresponding mononuclear [Ru(tpy)(bpy)(BNAH-H+)](+). (c) 2005 Elsevier B.V. All rights reserved.
• Creutz, Carol; Chou, Mei H., Journal of the American Chemical Society, 2009, vol. 131, p. 2794 - 2795
  作者：Creutz, Carol、Chou, Mei H.

  DOI：——

  日期：——