[Ru(2-phenylpyridine)(1,10-phenanthroline)(acetonitrile)₂]PF₆

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 菲咯啉
• 英文名称: [Ru(2-phenylpyridine)(1,10-phenanthroline)(acetonitrile)₂]PF₆
• 英文别名: [Ru(2-C6H4-2'-py-κC,N)(phen)(NCMe)₂]PF₆；[Ru(2-phenylpyridine)(acetonitrile)2(1,10-phenanthroline)]PF6；[Ru(2-phenylpyridine(1-))(1,10-phenanthroline)(MeCN)2]PF6；cis-[Ru(o-C6H4-2-py)(phen)(MeCN)2]PF6；[ruthenium(phenanthroline)(κ-C,N-(2-phenyl-pyridine)(NCMe)2]PF6；cis-[Ru(2-phenylpyridine-H)(1,10-phenanthroline)(MeCN)2]PF6；acetonitrile;1,10-phenanthroline;2-phenylpyridine;ruthenium(2+);hexafluorophosphate
• 化学式: C₂₇H₂₂N₅Ru*F₆P
• 分子量: 662.539
• InChiKey: BQISFVLVLNTMJS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.77
• 重原子数：
  40
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.07
• 拓扑面积：
  86.2
• 氢给体数：
  0
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  [Ru(2-phenylpyridine)(1,10-phenanthroline)(acetonitrile)₂]PF₆ 以 二氯甲烷 、 乙腈 为溶剂， 反应 72.0h， 以80%的产率得到[Ru(2-C₆H₄-2'-py-κC,N)(phen)(NCMe)₂]PF₆
  参考文献：
  名称：

  杂三（螯合物）钌配合物的合成合理的[Ru II（2-PH-2'-PY）（L ∧ L）（L' ∧ L'）] PF 6通过配体的反式选择性取代的Ruthenated苯环

  摘要：

  [Ru（N∧N）（MeCN）2（2-Ph-2'-Py）] PF 6（2-Ph-2'-Py =正金属化的2-苯基吡啶，N∧N =菲咯啉，2,2 '联吡啶），其中所述N个的氮之一∧ ñ配体结合到茹反式2-PhPy的苯基单元，缓慢异构化（2天）在回流的1,1-二氯乙烷/ MeCN中（9 / 1）或在紫外光存在下更快地（尽管收率降低），得到其中相同的N原子与Ru反式结合到2-PhPy的吡啶上的化合物；这些新化合物与它们的众所周知的异构体相反，被其他双齿含N的配体（例如4,4'-R 2）证明对MeCN配体的取代反应具有很好的反应性-2，2′-联吡啶（R ＝ H，OMe，COOH）和4，7-二甲基-1，10-菲咯啉。这些结果质疑了已经报道的从相同的起始原料中获得的杂配的三（螯合物）Ru II配合物的确切结构，在该起始原料中错误地认为传入的二齿配体在与N原子交叉的位置上与Ru原子结合。

  DOI：

  10.1021/om400611t
• 作为产物：
  描述：

  [Ru(NCMe)4(C6H4-2-C5H4N)]PF6 、 1,10-菲罗啉 以 乙腈 为溶剂， 以83%的产率得到[Ru(2-phenylpyridine)(1,10-phenanthroline)(acetonitrile)₂]PF₆
  参考文献：
  名称：

  Synthesis, Characterization, and Electrochemistry of Biorelevant Photosensitive Low-Potential Orthometalated Ruthenium Complexes

  摘要：

  Redox potentials of photosensitive cyclometalated Ru" derivatives of 2-phenylpyridine or 2-(4-tolyl)pyridine are controllably decreased by up to 0.8 V within several minutes. This is achieved by irradiation of the ruthena(II)cycles cis-[Ru(o-X-2-py)(LL)(MeCN)(2)]PF6 (2, X = C6H4 (a) or 4-MeC6H3 (b), LL = 1,10-phenanthroline or 2,2'-bipyridine). The cis geometry of the MeCN ligands has been confirmed by the X-ray structural studies. The sigma-bound sp(2) carbon of the metalated ring is trans to LL nitrogen. Complexes 2 are made from [Ru(o-X-2-py)(MeCN)(4)]PF6 (1) and I-L. This "trivial" ligand substitution is unusual because la reacts readily with phen in MeCN as solvent to give cis-[Ru(o-C6H4-2-py)(phen)(MeCN)(2)]PF6 (2c) in a 83% yield, but bpy does not afford the bpy-containing 2 under the same conditions. cis-[Ru(o-C6H4-2-py)(bpy)(MeCN)(2)]PF6 (2e) has been prepared in CH2Cl2 (74%). Studies of complexes 2c,e by cyclic voltammetry in MeOH in the dark reveal Ru-II/III quasy-reversible redox features at 573 and 578 mV (vs Ag/AgCl), respectively. A minute irradiation 2c and 2e converts them into now species with redox potentials of -230 and 270 mV, respectively. An exceptional potential drop for 2c is accounted for in terms of a photosubstitution of both MeCN ligands by methanol. ESR, H-1 NMR, and UV-vis data indicate that the primary product of photolysis of 2c is an octahedral monomeric low-spin (S = 112) Ru-III species, presumably cis-[Ru-II(o-C6H4-2-py)(phen)(MeOH)2]2+. The primary photoproduct of bpy complex 2e is cis-[Ru-II(O-C6H4-2-py)(bpy)(MeCN)(MeOH)](+), and this accounts for a lower decrease in the redox potential. Irradiation of 2c in the presence of added chloride affords [(phen)(o-C6H4-2-py)(ClRuORuCl)-O-III-Cl-IV(o-C6H4-2-py)(phen)]PF6, a first mu-oxo-bridged mixed valent dimer with a cyclometalated unit. The structure of the dimer has been established by X-ray crystallography.

  DOI：

  10.1021/ic048270w

文献信息

• Synthesis, Characterization, and Electrochemistry of Biorelevant Photosensitive Low-Potential Orthometalated Ruthenium Complexes
  作者：Alexander D. Ryabov、Ronan Le Lagadec、Hebert Estevez、Ruben A. Toscano、Simon Hernandez、Larissa Alexandrova、Viktoria S. Kurova、Andreas Fischer、Claude Sirlin、Michel Pfeffer

  DOI：10.1021/ic048270w

  日期：2005.3.1

  Redox potentials of photosensitive cyclometalated Ru" derivatives of 2-phenylpyridine or 2-(4-tolyl)pyridine are controllably decreased by up to 0.8 V within several minutes. This is achieved by irradiation of the ruthena(II)cycles cis-[Ru(o-X-2-py)(LL)(MeCN)(2)]PF6 (2, X = C6H4 (a) or 4-MeC6H3 (b), LL = 1,10-phenanthroline or 2,2'-bipyridine). The cis geometry of the MeCN ligands has been confirmed by the X-ray structural studies. The sigma-bound sp(2) carbon of the metalated ring is trans to LL nitrogen. Complexes 2 are made from [Ru(o-X-2-py)(MeCN)(4)]PF6 (1) and I-L. This "trivial" ligand substitution is unusual because la reacts readily with phen in MeCN as solvent to give cis-[Ru(o-C6H4-2-py)(phen)(MeCN)(2)]PF6 (2c) in a 83% yield, but bpy does not afford the bpy-containing 2 under the same conditions. cis-[Ru(o-C6H4-2-py)(bpy)(MeCN)(2)]PF6 (2e) has been prepared in CH2Cl2 (74%). Studies of complexes 2c,e by cyclic voltammetry in MeOH in the dark reveal Ru-II/III quasy-reversible redox features at 573 and 578 mV (vs Ag/AgCl), respectively. A minute irradiation 2c and 2e converts them into now species with redox potentials of -230 and 270 mV, respectively. An exceptional potential drop for 2c is accounted for in terms of a photosubstitution of both MeCN ligands by methanol. ESR, H-1 NMR, and UV-vis data indicate that the primary product of photolysis of 2c is an octahedral monomeric low-spin (S = 112) Ru-III species, presumably cis-[Ru-II(o-C6H4-2-py)(phen)(MeOH)2]2+. The primary photoproduct of bpy complex 2e is cis-[Ru-II(O-C6H4-2-py)(bpy)(MeCN)(MeOH)](+), and this accounts for a lower decrease in the redox potential. Irradiation of 2c in the presence of added chloride affords [(phen)(o-C6H4-2-py)(ClRuORuCl)-O-III-Cl-IV(o-C6H4-2-py)(phen)]PF6, a first mu-oxo-bridged mixed valent dimer with a cyclometalated unit. The structure of the dimer has been established by X-ray crystallography.
• DNA Binding to an Anticancer Organo-Ruthenium Complex
  作者：Marcelina Klajner、Pascal Hebraud、Claude Sirlin、Christian Gaiddon、Sebastien Harlepp

  DOI：10.1021/jp1044783

  日期：2010.11.11

  Because many anticancer drugs interact with DNA, the determination of their association constants to DNA is essential for quantifying their mechanisms of action. The interactions between a new ruthenium-derived compound [ruthenium(phenanthroline)(kappa-C,N-(2-phenyl-pyridine)(NCMe)(2)PF6, called RDCII] and DNA are studied using different techniques. Fluorescent experiments are used to determine the association and dissociation constants under different salt concentrations. The binding is shown to be reversible and noncovalent. The association constants vary from 1.5 x 10(6) M-1 to 2.9 x 10(3) M-1 when increasing the sodium concentration from 0.1 to 200 mM. Single-molecule stretching methods are used to study the interaction of RDC with longer DNA strands (8.6 kbp home-built dimer of pBR322). The affinities of RDC with DNA under different loads are obtained using McGhee and von Hippel analysis. The affinity constant and thermodynamic parameters are in good agreement with the values found in the literature and lead to the conclusion that this molecule intercalates dsDNA.
• Unusual phenomenon in the chemistry of orthometalated ruthenium (II) complexes
  作者：Alexander D. Ryabov、Hebert Estevez、Larissa Alexandrova、Michel Pfeffer、Ronan Le Lagadec

  DOI：10.1016/j.ica.2005.05.034

  日期：2006.2

  Yellow cyclometalatated ruthenium (II) complexes [Ru(o-X-2-py)(MeCN)(4)1PF(6) (1, X = C6H4 (a) or 4-MeC6H3 (b)) react readily with 1,10-phenanthroline (LL) in MeCN to give brownish-red species cis-[Ru(o-X-2-py)(LL)(MeCN)(2)]PF6 in high yields. The same reaction of the same complexes under the same conditions with 2,2'-bipyridine results in a significant color change from yellow to brownish-orange suggesting a formation of new species. Surprisingly, X-ray structural studies of these two complexes showed that they are structurally indistinguishable from the starting complexes 1. Referred to as complexes 4a,b, the new compounds are slightly more stable in the air though their spectral characteristics in solution are similar to 1a,b. The diffuse reflectance spectroscopy is so far the only technique that indicated differences between I and 4. (c) 2005 Elsevier B.V. All rights reserved.
• Rational Synthesis of Heteroleptic Tris(chelate) Ruthenium Complexes [Ru^II(2-Ph-2′-Py)(L^∧L)(L′^∧L′)]PF₆ by Selective Substitution of the Ligand Trans to the Ruthenated Phenyl Ring
  作者：Bastien Boff、Moussa Ali、Larissa Alexandrova、Noel Ángel Espinosa-Jalapa、Rafael Omar Saavedra-Díaz、Ronan Le Lagadec、Michel Pfeffer

  DOI：10.1021/om400611t

  日期：2013.9.23

  the same N atom was bound to Ru trans to the pyridine of 2-PhPy; these new compounds, in opposition to their well-known isomers, proved to be nicely reactive toward substitution reactions of the MeCN ligands, by other bidentate N-containing ligands such as 4,4′-R2-2,2′-bipyridine (R = H, OMe, COOH) and 4,7-dimethyl-1,10-phenanthroline. These results question the exact structure of the already reported

  [Ru（N∧N）（MeCN）2（2-Ph-2'-Py）] PF 6（2-Ph-2'-Py =正金属化的2-苯基吡啶，N∧N =菲咯啉，2,2 '联吡啶），其中所述N个的氮之一∧ ñ配体结合到茹反式2-PhPy的苯基单元，缓慢异构化（2天）在回流的1,1-二氯乙烷/ MeCN中（9 / 1）或在紫外光存在下更快地（尽管收率降低），得到其中相同的N原子与Ru反式结合到2-PhPy的吡啶上的化合物；这些新化合物与它们的众所周知的异构体相反，被其他双齿含N的配体（例如4,4'-R 2）证明对MeCN配体的取代反应具有很好的反应性-2，2′-联吡啶（R ＝ H，OMe，COOH）和4，7-二甲基-1，10-菲咯啉。这些结果质疑了已经报道的从相同的起始原料中获得的杂配的三（螯合物）Ru II配合物的确切结构，在该起始原料中错误地认为传入的二齿配体在与N原子交叉的位置上与Ru原子结合。