trans-cis-cis-Ru(1-benzyl-2-(4'-methylphenylazo)imidazole)2Cl2 | 387876-74-6

• 英文名称: trans-cis-cis-Ru(1-benzyl-2-(4'-methylphenylazo)imidazole)2Cl2
• 英文别名: cis-trans-cis-dichloro-bis-[1-benzyl-2-(4-methyl-phenylazo)imidazole]ruthenium(II)；cis,trans,cis-dichlorobis[1-benzyl-2-(p-tolylazo)imidazole]ruthenium(II)；ctc-dichloro-bis(1-benzyl-2-(p-tolylazo)imidazole)ruthenium(II)；ctc-[RuCl2(p-CH3C6H4NNC3H2N2(CH2C6H5))2]；cis,trans,cis-ruthenium(II)Cl2-bis(1-benzyl-2-(p-Me-phenylazo)imidazole)；cis-trans-cis-Ru(1-benzyl-2-(4-tolylazo)imidazole)2Cl2；cts-[RuCl2(1-benzyl-2-(p-tolylazo)imidazole)2]
• CAS: 387876-74-6；544706-39-0
• 化学式: C₃₄H₃₂Cl₂N₈Ru
• 分子量: 724.658
• InChiKey: ZEVLQCKUZAYBNV-ZELMBCLWSA-L

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：

  [Ag(phen)2]ClO4 、 trans-cis-cis-Ru(1-benzyl-2-(4'-methylphenylazo)imidazole)2Cl2 、 sodium perchlorate 以 甲醇 、 水 、 丙酮 为溶剂， 生成 [(1,10-phenanthroline)-bis-(1-benzyl-2-(p-methylphenylazo)imidazole)ruthenium(II)] perchlorate
  参考文献：
  名称：

  The synthesis, spectral studies and electrochemistry of 1,10-(phenanthroline)-bis-{1-alkyl-2-(arylazo)imidazole}ruthenium(II) perchlorate. Single crystal X-ray structure of [Ru(phen)(HaaiMe)2](ClO4)2 [phen=1,10-phenanthroline, HaaiMe=1-methyl-2-(phenylazo)imidazole]

  摘要：

  The hetero-tris-chelates of the formulae [Ru(phen)(RaaiR')(2)](ClO4)(2) [phen = 1,10-phenanthroline, RaaiR'= 1-alkyl-2-(arylazo)i-midazole, p-R-C6H4-N=N-C3H2-NN-1-R', where R = H (a), Me (b), Cl (c) and R'= Me (2), Et (3), CH(2)ph (4)} have been isolated from the reaction of ctc-[RuCl2(RaaiR')(2)] with AgNO3+phen or [Ag(phen)(2)](ClO4) in acetone at 40 degreesC in the dark followed by the addition of NaClO4(aq). The structure of [Ru(phen)(HaaiMe)(2)](ClO4)(2) has been confirmed by X-ray diffraction study and suggested stereoretentive nucleophilic substitution. The structure and stereochemistry of the complexes have been supported by H-1 NMR data. Electronic spectra exhibit a strong metal-to-ligand charge transfer (MLCT) band at 515-530 nm along with a weak transition at 700-710 nm. Cyclic voltammograms show a Ru(III)/Ru(II) couple at 1.3-1.4 V versus saturated calomel electrode (SCE) along with three successive ligand reductions. The plot of the difference in potential of the first oxidation and reduction versus energy of the main MLCT band ((V) over bar (CT)) is linear. (C) 2003 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(03)00004-4
• 作为产物：
  描述：

  水合三氯化钌 、 1-benzyl-2-(4'-methylphenylazo)imidazole 以 乙醇 为溶剂， 生成 trans-cis-cis-Ru(1-benzyl-2-(4'-methylphenylazo)imidazole)2Cl2 、 trans-cis-cis-Ru(1-benzyl-2-(4'-methylphenylazo)imidazole)2Cl2
  参考文献：
  名称：

  Chemistry of Azoimidazoles: Synthesis, Spectral Characterization, Electrochemical Studies, and X-ray Crystal Structures of Isomeric Dichloro Bis[1-alkyl-2-(arylazo)imidazole] Complexes of Ruthenium(II)

  摘要：

  Several new ligands, azoimidazoles belonging to the class 1-methyl-2-(arylazo)imidazoles (L-1 (3)) and 1-benzyl 2-(arylazo)imidazoles (L-2 (4)) (R = H (a), Me (b), OMe (c), Cl (d), NO2 (e)) have been synthesized and reacted with RuCl3 in ethanol under refluxing conditions. Two isomers of the composition RuL2Cl2, green (i) and blue (iii): are chromatographically separated. The green isomer is quantitatively transformed to the blue isomer on refluxing in a high boiling solvent. The isomeric structures have been confirmed by X-ray crystallography. Crystal data are as follows. Green complex C38H34Cl2N8Ru (6a): crystal system monoclinic; space group C2/c; a 15.650(8) Angstrom; b = 22.766(14) Angstrom: c = 11.473(5) Angstrom: beta = 119.27(4)degrees; V = 3573(3) Angstrom(3) Z = 4; R = 3.59%; R-w = 4.38%. Blue complex C22H24Cl2N8Ru(7b): crystal system monoclinic; space group P2(1)/n, a = 9.547(6) Angstrom; b = 22.554(14) Angstrom; c = 11.745(8) Angstrom: beta = 99.07(5)degrees; V = 2498(3) Angstrom(3); Z = 4; R = 3.15%; R-w = 4.51%. With reference to the pairs of Cl, N(imidazole), and N(azo) bound to Ru, the green isomer (6a) has a trans-cis-cis configuration and the blue isomer (7b) is cis-trans-cis. In both structures the Ru-N(azo) distances are relatively shorter than Ru-N(imidazole). indicating stronger bonding in the former and the presence of a Ru-L pi-interaction that is localized in the Ru-azo fragment. The isomer configuration is supported by IR and H-1 NMR data. The compounds exhibit t(2)(Ru) --> pi*(L) MLCT transitions in the visible region. Redox studies show the Ru(TLI)/Ru(II) couple in the green complexes (5, 6) at 0.6-0.7 V and in the blue complexes at 0.7-0.8 V versus SCE and two successive e azo reductions. The difference in the first metal and ligand redox potentials is linearly correlated with nu(CT) (t(2)(Ru) --> pi*(L).

  DOI：

  10.1021/ic970446p

文献信息

• Heteroleptic tris-chelates of ruthenium(ii)-bipyridine-arylazoimidazoles: Synthesis, spectral characterisation and electrochemical properties. Single crystal X-ray structure of [(2,2′-bipyridine)-bis-{1-methyl-2-(p-tolylazo)imidazole}ruthenium(ii)] perchlorate
  作者：Prithwiraj Byabartta、Joydev Dinda、Prasanta Kumar Santra、Chittaranjan Sinha、Kaliyamoorthy Panneerselvam、Fan-Ling Liao、Tian-Huey Lu

  DOI：10.1039/b103782j

  日期：——

  The reaction of cis-trans-cis-RuCl2(RaaiR′)2 [RaaiR′ = 1-alkyl-2-(arylazo)imidazole, p-R–C6H4–NN–C3H2–NN-1-R′, where R = H (a), Me (b), Cl (c) and R′ = Me (1), Et (2) and CH2Ph (3)] either with 2,2′-bipyridine (bpy) and AgNO3 followed by NaClO4 or [Ag(bpy)2](ClO4) in boiling acetone led to red-brown [Ru(bpy)(RaaiR′)2](ClO4)2. The complex may exist in three isomeric structures. The structure of [Ru(bpy)(MeaaiMe)2](ClO4)2 was confirmed by X-ray diffraction study and suggests that only one isomer is crystallised. Electronic spectra exhibit a strong MLCT band at 520 ± 5 nm along with two weak transitions at longer wavelength. The complexes emit at 77 K and quantum yields vary from 0.011–0.025. The 1H NMR spectral measurements of the complexes suggest the existence of two isomers in 1 ∶ 0.3 concentration ratio. The methylene, –CH2–, in RaaiEt of [Ru(bpy)(RaaiEt)2]2+ gives a complex AB type multiplet while the RaaiCH2Ph moiety of [Ru(bpy)(RaaiCH2Ph)2]2+ shows AB type quartets. Cyclic voltammograms show a Ru(III)/Ru(II) redox couple along with three successive ligand reductions. The plot of difference in potential of first oxidation and reduction versus energy of main MLCT band (CT) is linear. Electrochemical parametrization of the Ru(III)/Ru(II) redox couple determines ligand potential EL(L). Using EL(L) the potential of the present complexes has been predicted and is linearly related to the observed potential.

  cis-trans-cis-RuCl2(RaaiR²)2 [RaaiR² = 1-烷基-2-(芳基偶氮)咪唑，p-R–C6H4–NN–C3H2–NN-1-R²，其中 R = H (a), Me (b), Cl (c) 和 R² = Me (1), Et (2) 和 Ph (3)]与2,2′-联吡啶 (bpy) 及硝酸银 (AgNO3)，然后加氯酸钠 (Na ) 或在沸腾的丙酮中使用 [Ag(bpy)2](ClO4) 反应，得到了红棕色的 [Ru(bpy)(RaaiR²)2]( )2。该配合物可能存在三种异构体结构。通过 X 射线衍射研究确认了 [Ru(bpy)(MeaaiMe)2]( )2 的结构，表明只有一种异构体结晶。电子光谱在 520 ± 5 nm 处显示出强 MLCT 带，以及两个在更长波长处的弱跃迁。该配合物在 77 K 下发光，量子产率在 0.011–0.025 之间。配合物的 1H NMR 光谱测量表明存在两个异构体，其浓度比为 1 : 0.3。 [Ru(bpy)(RaaiEt)2]2+ 中 RaaiEt 的亚甲基 (–CH2–) 给出了复杂的 AB 型多重峰，而 [Ru(bpy)(Raai Ph)2]2+ 中的 Raai Ph 部分则显示 AB 型四重峰。循环伏安图显示出 Ru(III)/Ru(II) 的氧化还原对以及三个连续的配体还原。首次氧化与还原的电位差与主要 MLCT 带 (CT) 能量的关系图呈线性关系。Ru(III)/Ru(II) 的电化学参数化确定了配体电位 EL(L)。利用 EL(L)，预测了当前配合物的电位，并与观察到的电位呈线性关系。
• Ruthenium(II) phenylazopyridinearylazoimidazoles: Synthesis, spectral studies and redox properties
  作者：P. Byabartta

  DOI：10.1134/s1070328408030123

  日期：2008.3

  Tris-chelate complex [Ru(Pap)(RAaiR′)2](ClO4)2 (I, II, III/a, b, c) (where RAaiR′ = 1-alkyl-(2-arylazo)imidazole, R = H, Me, Cl (a, b, c); R′ = Me, Et, CH2Ph (I, II, III), and Pap = phenylazopyridine) was prepared by silver assisted synthetic route. IR spectra of the complexes support Ru-azo nitrogen π-bonding interaction. 1H NMR spectra suggest that there are two types of streochemical orientation of RAaiR′ around ruthenium(II). Cyclic voltammetry of the complexes shows one metal oxidation Ru(II)/Ru(III) at 1.4–1.5 V and three successive ligand reduction couples at the negative side of the reference potential in the range from −0.5 to −0.56, −0.7 to −0.8, and from −1.25 to −1.40 V, respectively.

  通过银辅助合成路线制备了三螯合物[Ru(Pap)(RAaiR′)2](ClO4)2（I、II、III/a、b、c）（其中 RAaiR′ = 1-烷基-(2-芳基偶氮)咪唑，R = H、Me、Cl（a、b、c）；R′ = Me、Et、CH2Ph（I、II、III），Pap = 苯并吡啶）。配合物的红外光谱支持 Ru-偶氮π键相互作用。1H NMR 光谱表明 RAaiR′ 围绕钌（II）有两种链化取向。配合物的循环伏安法显示，在 1.4-1.5 V 的电压下有一个金属氧化 Ru(II)/Ru(III)，而在参考电位的负侧则有三个连续的配体还原偶联，范围分别为 -0.5 至 -0.56、-0.7 至 -0.8，以及 -1.25 至 -1.40 V。
• First example of ruthenium–azoimine–chloranilates: synthesis, structure, spectra and electrochemistry of ruthenium(II) 1-alkyl-2-(arylazo)imidazole chloranilates, and correlation of electronic properties with ZINDO calculation
  作者：Sk. Jasimuddin、Prithwiraj Byabartta、Chittaranjan Sinha、Golam Mostafa、Tian-Huey Lu

  DOI：10.1016/j.ica.2003.11.040

  日期：2004.5

  Ru(R–aai–R ′ ) 2 Cl 2 followed by the reaction with chloranilic acid (H 2 CA) in presence of Et 3 N gives a neutral mononuclear violet complex [Ru(R–aai–R ′ ) 2 (CA)]. [R–aai–R ′ = p -R–C 6 H 4 –NN–C 3 H 2 –NN–1-R ′ , abbreviated as N , N ′ chelator, where N(imidazole) and N(azo) represent N and N ′ , respectively; R=H ( a ), Me ( b ), Cl ( c ) and R ′ =Me ( 4 ), Et ( 5 ), CH 2 Ph ( 6 )]. The structure

  Ag +辅助的蓝色顺式-反式-顺式Ru（R–aai–R'）2 Cl 2的脱氯，然后在Et 3 N存在下与氯酸（H 2 CA）反应，得到中性的单核紫罗兰络合物[Ru （R–aai–R'）2（CA）]。[R–aai–R'= p -R–C 6 H 4 –NN–C 3 H 2 –NN–1-R'，缩写为N，N'螯合剂，其中N（咪唑）和N（偶氮）分别代表N和N'; R ＝ H（a），Me（b），Cl（c）和R′＝ Me（4），Et（5），CH 2 Ph（6）]。通过X射线衍射研究确定了一种情况下的结构[Ru（Cl–aai–Et）2（CA）]。π-π堆积和H键网络给出了超分子阶梯。所有复合物在可见光区域均表现出强烈的MLCT跃迁，而在较高波长（> 700 nm）中表现出较弱的宽带。可见的跃迁（580-595 nm）显示出负变色效应。循环伏安图显示了在SCE处为正的两个准可逆至不可逆偶，这是由于CA-/
• Ruthenium(II)-arylazoimidazole-8-hydroxyquinolinate complexes: Synthesis, spectral study (H, C, COSY, HMQC-NMR) and redox properties
  作者：P. Byabartta

  DOI：10.1134/s0036023609090101

  日期：2009.9

  The reaction of [Ru(OH2)(2)(RaaiR')(2)](2+) (RaaiR' = 1-alkyl-2-(arylazo)imidazole, p-R-C6H4-N=N-C3H2NN(1)-R', R = H (1), Me (2), Cl (3); R' = Me (a), Et (b), CH2Ph (c)) with 8-quinolinol (HQ) in acetone solution followed by the addition of NH4PF6 has afforded violet coloured mixed ligand complexes of the composition [Ru(Q)(RaaiR')(2)](PF6). The maximum molecular peak of 1b is observed at m'z 790 (50%) in the ESI mass spectrum. Ir spectra of the complexes show -C=N- and -N=N- stretching near at 1590 and 1370 cm(-1). The H-1 NMR spectral measurements suggest methylene, -CH2-, in RaaiEt gives a complex AB type while in RaaiCH(2)Ph it shows AB type quartets. Considering the arylazoimidazole and oxine moitie there are twenty different carbon atoms in the molecule which gives a total of twenty different peaks in the C-13 NMR spectrum of complex 1a. In the H-1-H-1 COSY spectrum of the present complexes, absence of any off-diagonal peaks extending from delta = 14.12 and 9.55 ppm confirm their assignment of no proton on N(1) and N(3) respectively. Contour peaks in the H-1-C-13 HMQC spectrum in the present complexes, the absence of any contours at delta = 157.12, 160.76, 155.67 ppm and 157.68-160.2 ppm assign them to the C(2), C(6), C(g) and C(h), C(i) carbon atoms respectively. The solution structure and stereoretentive transformation in each step have been established from n.m.r. results. Cyclic voltammograme show a Ru(III)/Ru(II) couple at 1.0-1.1 V versus SCE along with three successive ligand reductions.
• 1,10-(phenanthroline)-bis{1-alkyl-2-(arylazo)imidazole} ruthenium(II) perchlorate: Synthesis, spectral study, and electrochemistry
  作者：P. Byabartta

  DOI：10.1134/s1070328409080053

  日期：2009.8

  The hetero-tris-chelates of the formula [Ru(Phen)(RAaiR')(2)](ClO4)(2) (Phen = 1,10-phenanthroline, RAaiR' = 1-alkyl-2-(arylazo)imidazole, p-R-C6H4-N=N-C3H2-NN-1-R', where R = H (a), Me (b), Cl (c) and R' = Me (II), Et (III), CH2Ph (IV)) have been isolated from the reaction of ctc-[RuCl2(RAaiR')(2)] with AgNO3 + Phen or [Ag(Phen)(2)](ClO4) in acetone at 40A degrees C in dark followed by the addition of NaClO4 (aq). The stereo-chemistry of the complexes have been supported by H-1 NMR data. Considering the arylazoimidazole and phenanthroline moietie there are twenty different carbon atoms in the molecule which gives a total of twenty different peaks in the C-13 NMR spectrum of complex Ia. Cyclic voltammograms show Ru(III)/Ru(II) couple at 1.3-1.4 V vs SCE along with three successive ligand reductions.