bis(2,2':6',2''-terpyridine)ruthenium(II) | 24414-01-5

• 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: bis(2,2':6',2''-terpyridine)ruthenium(II)
• 英文别名: bis(2,2':6',2''-terpyridine)ruthenium(II)(2+)；[Ru(2,2':6',2''-terpyridine)2](2+)；Ru(2,2':6',2''-terpyridine)2(2+)；bis(terpyridine)ruthenium(II)；(terpyridyl)2Ru(2+)；{Ru(tpy)2}(2+)；2,6-Dipyridin-2-ylpyridine;ruthenium(2+)
• CAS: 24414-01-5
• 化学式: C₃₀H₂₂N₆Ru
• 分子量: 567.615
• InChiKey: DGNCBZYLYCIDCN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.41
• 重原子数：
  37
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  77.3
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  盐酸 、 bis(2,2':6',2''-terpyridine)ruthenium(II) 以 氘代乙腈 为溶剂， 生成 [Ru(tpy)₂]Cl₂
  参考文献：
  名称：

  Enhancing the Anion Affinity of Urea-Based Receptors with a Ru(terpy)₂²⁺ Chromophore

  摘要：

  Covalent linking of a Ru(terpy)(2)(2+) substituent improves recognition and sensing properties of the urea subunit toward anions. Urea's anion affinity is enhanced by the electrostatic attraction exerted by the Ru-II cation and by the electron-withdrawing effect exerted by the entire polypyridine-metal complex. Such an enhancement of the anion affinity, which results from the combination of a through-space and a through-bond effect, is greater than that exerted by the classical neutral electron-withdrawing substituent nitrophenyl. Small yet significant modifications of pi-pi* and MLCT bands of the Ru(terpy)(2)(2+) chromophore, detected through UV-vis spectrophotometric titrations, allowed the determination of the constants for the formation of receptor-anion H-bond complexes in diluted MeCN solution. On H-1 NAIR titration experiments, carried out under more concentrated conditions, the interaction of a second Cl- ion was observed, taking place through an outer-sphere mechanism. The Ru(terpy)(2)(2+) substituent favors the deprotonation of a urea N-H fragment on addition of a second equivalent of fluoride, with formation of HF2-.

  DOI：

  10.1021/ic400196a
• 作为产物：
  描述：

  α,α,α-三联吡啶 、 [ruthenium(II)(η⁶-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]₂ 以 乙醇 、 水 为溶剂， 以90%的产率得到bis(2,2':6',2''-terpyridine)ruthenium(II)
  参考文献：
  名称：

  基于联吡啶和联吡啶的钌配合物作为Belousov-Zhabotinsky反应的催化剂

  摘要：

  我们报道了在Belousov-Zhabotinsky（BZ）振荡化学反应中成功使用Ru（II）（terpy）2（1，terpy = 2,2'：6'，2''-叔吡啶）作为催化剂。我们还研究了另外几种Ru（II）络合物，Ru（II）（bipy）2（L'）2（2，L'= 4-吡啶羧酸; bipy = 2,2'-bipyridine）和Ru（II）（ bipy）2（L''）（3，L''= 4,4'-di羧基-2,2'-bipy; 4，L''= N-烯丙基-4'-甲基-[2,2'- bipy] -4-carboxamide; 5，L''= bipy），用于催化BZ反应。虽然2不能触发BZ振荡，可能是由于BZ溶液中L'的快速损失，其他基于联吡啶的Ru（II）络合物可以催化BZ反应，尽管它们的催化活性受到缓慢的配体取代的不利影响。 BZ解决方案。尽管如此，成功测试的Ru（II）（terpy）2和Ru（I

  DOI：

  10.1021/jp111724t

文献信息

• Optimising the synthesis, polymer membrane encapsulation and photoreduction performance of Ru(ii)- and Ir(iii)-bis(terpyridine) cytochrome c bioconjugates
  作者：David Hvasanov、Alexander F. Mason、Daniel C. Goldstein、Mohan Bhadbhade、Pall Thordarson

  DOI：10.1039/c3ob40620b

  日期：——

  Ruthenium(II) and iridium(III) bis(terpyridine) complexes were prepared with maleimide functionalities in order to site-specifically modify yeast iso-1 cytochrome c possessing a single cysteine residue available for modification (CYS102). Single X-ray crystal structures were solved for aniline and maleimide Ru(II) 3 and Ru(II) 4, respectively, providing detailed structural detail of the complexes. Light-activated bioconjugates prepared from Ru(II) 4 in the presence of tris(2-carboxyethyl)-phosphine (TCEP) significantly improved yields from 6% to 27%. Photoinduced electron transfer studies of Ru(II)–cyt c in bulk solution and polymer membrane encapsulated specimens were performed using EDTA as a sacrificial electron donor. It was found that membrane encapsulation of Ru(II)–cyt c in PS140-b-PAA48 resulted in a quantum efficiency of 1.1 ± 0.3 × 10−3, which was a two-fold increase relative to the bulk. Moreover, Ir(III)–cyt c bioconjugates showed a quantum efficiency of 3.8 ± 1.9 × 10−1, equivalent to a ∼640-fold increase relative to bulk Ru(II)–cyt c.

  制备了含有马来酰亚胺功能的钌(II)和铱(III)双三吡啶配合物，以便在酵母同源1细胞色素c上，针对可用于修饰的单个半胱氨酸残基（CYS102）进行位点特异性修饰。分别解析了苯胺和马来酰亚胺钌(II) 3和钌(II) 4的单晶X射线晶体结构，提供了这些配合物的详细结构细节。在三(2-羧乙基)膦(TCEP)存在下，从钌(II) 4制备的光活化生物偶联物显著提高了产量，从6%增加到27%。在大量溶液和聚合物膜封装的样品中，使用EDTA作为牺牲电子供体，进行了钌(II)–细胞色素c的光诱导电子转移研究。发现将钌(II)–细胞色素c封装在PS140-b-PAA48膜中，量子效率为1.1 ± 0.3 × 10^−3，相对于大量溶液中的封装效率增加了两倍。此外，铱(III)–细胞色素c生物偶联物的量子效率为3.8 ± 1.9 × 10^−1，相当于相对于大量溶液中的钌(II)–细胞色素c提高了约640倍。
• Bis[4′-(4-anilino)-2,2′∶6′,2″- terpyridine]transition-metal complexes: electrochemically active monomers with a range of magnetic and optical properties for assembly of metallo oligomers and macromolecules
  作者：Gregory D. Storrier、Stephen B. Colbran、Donald C. Craig

  DOI：10.1039/a702778h

  日期：——

  The new ligand 4′-(4-anilino)-2,2′∶6′,2″-terpyridine (L 1 ) and a range of its transition-metal complexes have been prepared. The crystal and molecular structures of L 1 and [CuL 1 2 ][PF 6 ] 2 have been determined. Model reactions show that L 1 and its transition-metal complexes can be functionalised with suitable organic reagents: reactions with aromatic dianhydrides give imide derivatives, reactions with acid chlorides afford amide derivatives and benzoquinone reacts with L 1 to give a quinonylanilinoterpyridine ligand, complexes of which are described, but not with the complexes of L 1 . The use of L 1 and its complexes in building up multicomponent architectures has been tested. Metallo-dimers and co-ordination polymers linked by new binucleating bis(terpyridyl) ligands have been prepared by two routes: (a) first coupling two L 1 with difunctional organic reagents and then treating the new binucleating ligands with a metal source, or (b) preforming monomeric complexes of L 1 and treating these with the same difunctional organic reagents. Analytical, spectroscopic and electrochemical data are given for all complexes; the chromophoric, magnetic and electrochemical properties of the complexes vary with transition metal and terpyridyl ligand substituent.

  新配体4'-(4-氨基苯基)-2,2'-6',2''-三吡啶（L₁）及其一系列过渡金属络合物已被合成。已确定L₁和[CuL₁₂][PF₆]₂的晶体和分子结构。模型反应表明L₁及其过渡金属络合物可以与适当的有机试剂进行功能化：与芳香族二酸酐的反应生成酰亚胺衍生物，与酸氯化物的反应生成酰胺衍生物，而苯醌与L₁反应生成一个喹啉基苯胺三吡啶配体，其络合物的性质已被描述，但与L₁的络合物不同。已经测试L₁及其络合物在构建多组分架构中的应用。通过两条路线制备了新双核双（三吡啶）配体连接的金属二聚体和配位聚合物：（a）首先将两个L₁与双官能团有机试剂耦合，然后将新形成的双核配体与金属源反应，或（b）预先形成L₁的单体络合物，并使用相同的双官能团有机试剂进行处理。所有络合物的分析、光谱和电化学数据均有所提供；络合物的色谱、磁性和电化学性质随着过渡金属和三吡啶配体取代基的不同而变化。
• Synthesis, structures and electrochemical properties of ruthenium (II) complexes bearing bidentate 1,8-naphthyridine and terpyridine analogous (N,N,C)-tridentate ligands
  作者：Take-aki Koizumi、Takashi Tomon、Koji Tanaka

  DOI：10.1016/j.jorganchem.2005.06.033

  日期：2005.10

  (napy) and terpyridine-analogous (N,N,C) tridentate ligands coordinated ruthenium (II) complexes, [RuL(napy-κ2N,N′) (dmso)](PF6)2 (1: L=L1=N″-methyl-4′-methylthio-2,2′:6′,4″-terpyridinium, 2: L = L2 = N″-methyl-4′-methylthio-2,2′:6′,3″-terpyridinium) were prepared and their chemical and electrochemical properties were characterized. The structure of complex 1 was determined by X-ray crystallographic study

  1,8-萘啶（napy）和三联吡啶类似（N，N，C）的三齿配体配位的钌（II）配合物，[孺大号（napy-κ 2 Ñ，Ñ '）（DMSO）]（PF 6）2（1：L = L 1 = N ''-甲基-4'-甲硫基-2,2'：6'，4''-吡啶鎓2 ; L  =  L 2  =  N ''-甲基-4'-甲硫基-2，制备了2'：6'，3''-吡啶鎓），并对其化学和电化学性质进行了表征。配合物1的结构由X射线晶体学研究确定，表明它具有扭曲的八面体配位样式。DMF中1的循环伏安图显示了两个可逆的配体定位氧化还原对。在另一方面，的CV 2只显示了两个不可逆还原峰，由于在Ru-C键2含有carbenic字符。的红外光谱1在CO 2 -饱和CH 3 CN表明RU-的形成（η 1 -CO 2）在-1.44五之下溶液的控制电势电解和Ru-CO络合物（相对于Fc / Fc的+）。CO的电化学还原2催化1在-1.54
• Synthesis, characterization, and electrocatalytic oxidation of benzyl alcohol by a pair of geometric isomers of [Ru(trpy)(4,4′-Me2dppi)(OH2)]2+ where 4,4′-dppi is 3,6-di-(4-methylpyrid-2-yl)pyridazine
  作者：Vincent J Catalano*、Ryan A Heck、Anna Öhman、Michael G Hill*

  DOI：10.1016/s0277-5387(00)00347-8

  日期：2000.5

  Abstract The geometric isomers, in -[Ru(trpy)(4,4′-Me 2 dppi)Cl] + ( 1a ), in -[Ru(trpy)(4,4′-Me 2 dppi)OH 2 ] 2+ ( 1b ), and in -[Ru(trpy)(4,4′-Me 2 dppi)(NCCH 3 )] 2+ ( 1c ), out -[Ru(trpy)(4,4′-Me 2 dppi)Cl] + ( 2a ), out -[Ru(trpy)(4,4′-Me 2 dppi)OH 2 ] 2+ ( 2b ), and out -[Ru(trpy)(4,4′-Me 2 dppi)(NCCH 3 )] 2+ ( 2c ), where trpy is 2,2′,2″-terpyridine and 4,4′-Me 2 dppi is 3,6-di-(4-methylpyrid-2-yl)pyridazine

  摘要-[Ru（trpy）（4,4'-Me 2 dppi）Cl] +（1a）中的几何异构体-[Ru（trpy）（4,4'-Me 2 dppi）OH 2] 2 +（1b），和-[Ru（trpy）（4,4'-Me 2 dppi）（NCCH 3）] 2+（1c），输出-[Ru（trpy）（4,4'-Me 2 dppi ）Cl] +（2a），out-[Ru（trpy）（4,4'-Me 2 dppi）OH 2] 2+（2b），out-[Ru（trpy）（4,4'-Me 2 dppi）（NCCH 3）] 2+（2c），其中trpy是2,2'，2''-叔吡啶，而4,4'-Me 2 dppi是3,6-二-（4-甲基吡啶-2-基）哒嗪是合成的，并通过UV-Vis和1 H NMR光谱进行了表征。进出标记是指非亚胺基团的取向，其指向进复合物中的复合物的中心，而远离出复合物中的中心。化合物1a和2c还通过X射线晶体
• Synthesis, Structure, and Acid−Base and Redox Properties of a Family of New Ru(II) Isomeric Complexes Containing the Trpy and the Dinucleating Hbpp Ligands
  作者：Cristina Sens、Montserrat Rodríguez、Isabel Romero、Antoni Llobet、Teodor Parella、Jordi Benet-Buchholz

  DOI：10.1021/ic0346836

  日期：2003.12.1

  mononuclear geometrical isomers containing the ligand 3,5-bis(2-pyridyl)pyrazole (Hbpp) of general formula in- and out-[RuII(Hbpp)(trpy)X](n+) (trpy=2,2':6',2' '-terpyridine; X=Cl, n=1, 2a,b; X=H2O, n=2, 3a,b; X=py (pyridine), n=2, 4a,b) have been prepared through two different synthetic routes, isolated, and structurally characterized. The solid state structural characterization was performed by X-ray diffraction

  三对单核几何异构体，分别含有配体为内和外-[RuII（Hbpp）（trpy）X]（n +）的配体3,5-双（2-吡啶基）吡唑（Hbpp）（trpy = 2,2 '：6'，2''-吡啶; X = Cl，n = 1，2a，b; X = H2O，n = 2，3a，b; X = py（吡啶），n = 2，4a，b）已通过两种不同的合成路线（分离并进行结构表征）制备了这些化合物。固态结构表征是通过X射线衍射分析两种配合物：2a-4a和4b进行的。溶液的结构表征是通过1D和2D NMR光谱对配合物2a，b和4a，b进行的，并且与在固态下发现的结构一致。所有配合物还通过紫外可见分光光度法进行了表征，这也使我们能够进行分光光度酸碱滴定。因此，在光谱学上表征了许多物种，它们具有相同的氧化态但质子化程度不同。例如，对于3a，获得了三个pKa值：pKa1（RuII）= 2.13，pKa2（RuII）= 6.88和pKa3（RuII）=