Ru(II)Ru(III)Cl(O2C(C6H4-p-Me))4 | 139347-44-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: Ru(II)Ru(III)Cl(O2C(C6H4-p-Me))4
• 英文别名: Ru2Cl(O2CC6H4-p-Me)4；RuCl2(p-methylbenzoato)4；chlororuthenium(2+);4-methylbenzoate;ruthenium(2+)
• CAS: 139347-44-7
• 化学式: C₃₂H₂₈ClO₈Ru₂
• 分子量: 778.163
• InChiKey: IWWPNWUVICLFBE-UHFFFAOYSA-I

计算性质

• 辛醇/水分配系数(LogP)：
  2.12
• 重原子数：
  43
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  161
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  Ru(II)Ru(III)Cl(O2C(C6H4-p-Me))4 在 K₂S₂O₈ 作用下， 以 甲醇 、 水 为溶剂， 生成 [Ru2O(O2CC6H4-p-Me)2(1-methylimidazole)6](ClO4)3
  参考文献：
  名称：

  Synthesis, X-ray Structures, and Spectroscopic and Electrochemical Properties of (μ-Oxo)bis(μ-carboxylato)diruthenium Complexes Having Six Imidazole Bases as Terminal Ligands

  摘要：

  Complexes [Ru2O(O2CR)(2)(1-MeIm)(6)](ClO4)(2) (la-c), [Ru2O(O2CR)(2)(ImH)(6)](ClO4)(2) (2a,b), and [Ru2O(O2CR)(2)(4-MeImH)(6)](ClO4)(2) (3a,b) with a (mu-oxo)bis(mu-carboxylato)diruthenium(III) core have been prepared by reacting Ru2Cl(O2CR)(4) with the corresponding imidazole base, viz. 1-methylimidazole (1-MeIm), imidazole (ImH), and 4-methylimidazole (4-MeImH) in methanol, followed by treatment with NaClO4 in water (R: Me, a; C6H4-p-OMe, b; C6H4-p-Me, c). Diruthenium(III,IV) complexes [Ru2O(O2CR)(2)(1-MeIm)(6)](ClO4)(3) (R: Me, 4a; C6H4-p-OMe, 4b; C6H4-p-Me, 4c) have been prepared by one-electron oxidation of 1 in MeCN with K2S2O8 in water. Complexes la, 2a . 3H(2)O, and 4a . 1.5H(2)O have been structurally characterized. Crystal data for the complexes are as follows: la, orthorhombic, P2(1)2(1)2(1), a = 7.659(3) Angstrom, b = 22.366(3) Angstrom, c = 23.688(2) Angstrom, V = 4058(2) Angstrom(3), Z = 4, R = 0.0475, and R-w = 0.0467 for 2669 reflections with F-o > 2 sigma(F-o); 2a . 3H(2)O, triclinic, , a = 13.735(3) Angstrom, b = 14.428(4) Angstrom, c = 20.515(8) Angstrom, alpha = 87.13(3)degrees, beta = 87.61(3)degrees, gamma = 63.92(2)degrees, V = 3646(2) Angstrom(3), Z = 4, R = 0.0485 and R-w = 0.0583 for 10 594 reflections with F-o > 6 sigma(F-o); 4a . 1.5H(2)O triclinic, , a = 11.969(3) Angstrom, b = 12.090(6) Angstrom, c = 17.421(3) Angstrom, alpha = 108.93(2)degrees, beta = 84.42(2)degrees, gamma = 105.97(2)degrees, V = 2292(1) Angstrom(3), Z = 2, R = 0.0567, and R-w = 0.0705 for 6775 reflections with F-o > 6 sigma(F-o). The complexes have a diruthenium unit held by an oxo and two carboxylate ligands, and the imidazole ligands occupy the terminal sites of the core. The Ru-Ru distance and the Ru-O-oxo-Ru angle in la and 2a . 3H(2)O are 3.266(1), 3.272(1) Angstrom and 122.4(4), 120.5(2)degrees, while in 4a . 1.5H(2)O these values are 3.327(1) Angstrom and 133.6(2)degrees. The diruthenium(III) complexes 1-3 are blue in color and they exhibit an intense visible band in the range 560-575 nm. The absorption is charge transfer in nature involving the Ru(III)-d pi and O-oxo-p pi orbitals. The diruthenium(III,IV) complexes are red in color and show an intense band near 500 nm.The diruthenium(III) core readily gets oxidized with K2S2O8 forming quantitatively the diruthenium(III,IV) complex. The visible spectral record of the conversion shows an isosbestic point at 545 nm for 1 and at 535 nm for 2 and 3. Protonation of the oxide bridge by HClO4 in methanol yields the [Ru-2(mu-OH)(mu-O2CR)(2)](3+) core. The hydroxo species shows a visible band al 550 nm. The pK(a) value for la is 2.45. The protonated species are unstable. The 1-MeIm species converts to the diruthenium(III,IV) core, while the imidazole complex converts to [Ru(ImH)(6)](3+) and some uncharacterized products. Complex [Ru(ImH)(6)](ClO4)(3) has been structurally characterized. The diruthenium(III) complexes are essentially diamagnetic and show characteristic H-1 NMR spectra indicating the presence of the dimeric structure in solution. The diruthenium(III,IV) complexes are paramagnetic and display rhombic EPR spectral features. Complexes 1-3 are redox active. Complex 1 shows the one-electron reversible Ru-2(III)/(RuRuIV)-Ru-III, one-electron quasireversible (RuRuIV)-Ru-III/Ru-2(IV), and two-electron quasireversible Ru-2(III)/Ru-2(II) couples near 0.4, 1.5, and -1.0 V vs SCE In MeCN-0.1 M TBAP, respectively, in the cyclic and differential pulse voltammetric studies. Complexes 2 and 3 exhibit only reversible Ru-2(III)/(RuRuIV)-Ru-III and the quasireversible (RuRuIV)-Ru-III/Ru-2(IV) couples near 0.4 and 1.6 V vs SCE, respectively, The observation of a quasireversible one-step two-electron transfer reduction process in 1 is significant considering its relevance to the rapid and reversible Fe-2(III)/Fe-2(II) redox process known for the tribridged diiron core in the oxy and deoxy forms of hemerythrin.

  DOI：

  10.1021/ic970390z
• 作为产物：
  描述：

  tetraacetatodiruthenium chloride 、 对甲基苯甲酸 以 水 为溶剂， 反应 16.0h， 以93%的产率得到Ru(II)Ru(III)Cl(O2C(C6H4-p-Me))4
  参考文献：
  名称：

  制备四酰胺基和四羧酸二二钌化合物的不同方法的比较研究。结构和磁特性†

  摘要：

  溶剂热法和微波辅助合成法是绿色的且非常有用的替代方法，用于获得新的氯四酰胺基二钌化合物[Ru 2 Cl（μ-NHOCR）4 ] n [R = Me- o -C 6 H 4（1），Me- m -C 6 H 4（2），Me- p -C 6 H 4（3）]。类似tetracarboxylato络合物的[Ru 2 Cl（上μ-O 2 CR）4 ] Ñ [R = ME- ø -C 6 ħ在图4（ 4）中，还获得了Me m -C 6 H 4（ 5），Me- p -C 6 H 4（ 6）]。这些合成方法允许使用绿色溶剂，例如水 或者 乙醇。而且，溶剂热合成允许在合成过程中直接结晶所需的络合物，所述所需的络合物在普通溶剂中极不溶。因此，已经使用单晶X射线衍射建立了所有晶体的晶体结构。配合物1的Ru–Cl–Ru角为180°，是在固态下显示线性链的四氯化四氨基叠氮化二钌衍生物的第一个实例。相反，复合物2·0.

  DOI：

  10.1039/c2dt30939d

文献信息

• Das, Birinchi K.; Chakravarty, Akhil R., Inorganic Chemistry, 1992, vol. 31, # 8, p. 1395 - 1400
  作者：Das, Birinchi K.、Chakravarty, Akhil R.

  DOI：——

  日期：——
• Sudha, Chellamma; Chakravarty, Akhil R., Indian Journal of Chemistry, Section A: Inorganic, Physical, Theoretical and Analytical, <hi>1998</hi>, vol. 37, # 1, p. 1 - 6
  作者：Sudha, Chellamma、Chakravarty, Akhil R.

  DOI：——

  日期：——
• Das, Birinchi K.; Chakravarty, Akhil R., Inorganic Chemistry, <hi>1991</hi>, vol. 30, # 26, p. 4978 - 4986
  作者：Das, Birinchi K.、Chakravarty, Akhil R.

  DOI：——

  日期：——