Ruthenocene

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Nils Metzlernolte - One of the best experts on this subject based on the ideXlab platform.

  • a Ruthenocene pna bioconjugate synthesis characterization cytotoxicity and aas detected cellular uptake
    Bioconjugate Chemistry, 2012
    Co-Authors: Annika Gross, Nina Husken, Julia Schur, łukasz Raszeja, Nils Metzlernolte
    Abstract:

    Labeling of peptide nucleic acids (PNA) with metallocene complexes is explored herein for the modulation of the analytical characteristics, as well as biological properties of PNA. The synthesis of the first Ruthenocene–PNA conjugate with a dodecamer, mixed-sequence PNA is described, and its properties are compared to a ferrocene-labeled analogue as well as an acetylated, metal-free derivative. The synthetic characteristics, chemical stability, analytical and thermodynamic properties, and the interaction with cDNA were investigated. Furthermore, the cytotoxicity of the PNA conjugates is determined on HeLa, HepG2, and PT45 cell lines. Finally, the cellular uptake of the metal-containing PNAs was quantified by high-resolution continuum source atomic absorption spectrometry (HR-CS AAS). An unexpectedly high cellular uptake to final concentrations of 4.2 mM was observed upon incubation with 50 μM solutions of the Ruthenocene–PNA conjugate. The Ruthenocene label was shown to be an excellent label in all respec...

  • azidomethyl Ruthenocene facile synthesis of a useful metallocene derivative and its application in the click labelling of biomolecules
    Chemical Communications, 2011
    Co-Authors: Malay Patra, Nils Metzlernolte
    Abstract:

    A convenient synthesis of azidomethyl-Ruthenocene and its use in the covalent labelling of amino acids, peptides and a peptide nucleic acid (PNA) monomer derivative by Cu(I) catalyzed azide–alkyne coupling (Cu-AAC, “click chemistry”) are described.

Rainer F Winter - One of the best experts on this subject based on the ideXlab platform.

  • mixed valent Ruthenocene vinylruthenium conjugates valence delocalization despite chemically different redox sites
    Inorganic Chemistry, 2019
    Co-Authors: Christopher Hassenruck, Andre Mang, Rainer F Winter
    Abstract:

    Ruthenocene–vinylruthenium conjugates Rc/Rc*–CH═CH–Ru(CO)(L)(PiPr3)2 (Rc = (η5-C5H5)Ru(η5-C5H4); Rc* = (η5-C5Me5)Ru(η5-C5H4); L = Cl or κO,O′-acetylacetonato) have been prepared and investigated in their neutral, mono-, and dioxidized states by cyclic voltammetry, IR and UV/vis/NIR spectroelectrochemistry, and EPR spectroscopy. Their corresponding radical cations are (almost) completely delocalized mixed-valent systems as indicated by the low half-widths, the absence of solvatochromism, and the low-energy cutoff of their IVCT bands in the near-infrared (NIR) and their IR and EPR spectroscopic signatures. The degree of electronic coupling even exceeds that of their ferrocene analogs despite comparable differences between the intrinsic half-wave potentials of the vinylruthenium and the metallocenyl entities and substantially smaller half-wave potential splittings, ΔE1/2, in the Ruthenocene congeners. All experimental results are backed by quantum chemical calculations.

  • Mixed-Valent Ruthenocene–Vinylruthenium Conjugates: Valence Delocalization Despite Chemically Different Redox Sites
    Inorganic Chemistry, 2019
    Co-Authors: Christopher Hassenruck, Andre Mang, Rainer F Winter
    Abstract:

    Ruthenocene–vinylruthenium conjugates Rc/Rc*–CH═CH–Ru(CO)(L)(PiPr3)2 (Rc = (η5-C5H5)Ru(η5-C5H4); Rc* = (η5-C5Me5)Ru(η5-C5H4); L = Cl or κO,O′-acetylacetonato) have been prepared and investigated in their neutral, mono-, and dioxidized states by cyclic voltammetry, IR and UV/vis/NIR spectroelectrochemistry, and EPR spectroscopy. Their corresponding radical cations are (almost) completely delocalized mixed-valent systems as indicated by the low half-widths, the absence of solvatochromism, and the low-energy cutoff of their IVCT bands in the near-infrared (NIR) and their IR and EPR spectroscopic signatures. The degree of electronic coupling even exceeds that of their ferrocene analogs despite comparable differences between the intrinsic half-wave potentials of the vinylruthenium and the metallocenyl entities and substantially smaller half-wave potential splittings, ΔE1/2, in the Ruthenocene congeners. All experimental results are backed by quantum chemical calculations.

Annika Gross - One of the best experts on this subject based on the ideXlab platform.

  • a Ruthenocene pna bioconjugate synthesis characterization cytotoxicity and aas detected cellular uptake
    Bioconjugate Chemistry, 2012
    Co-Authors: Annika Gross, Nina Husken, Julia Schur, łukasz Raszeja, Nils Metzlernolte
    Abstract:

    Labeling of peptide nucleic acids (PNA) with metallocene complexes is explored herein for the modulation of the analytical characteristics, as well as biological properties of PNA. The synthesis of the first Ruthenocene–PNA conjugate with a dodecamer, mixed-sequence PNA is described, and its properties are compared to a ferrocene-labeled analogue as well as an acetylated, metal-free derivative. The synthetic characteristics, chemical stability, analytical and thermodynamic properties, and the interaction with cDNA were investigated. Furthermore, the cytotoxicity of the PNA conjugates is determined on HeLa, HepG2, and PT45 cell lines. Finally, the cellular uptake of the metal-containing PNAs was quantified by high-resolution continuum source atomic absorption spectrometry (HR-CS AAS). An unexpectedly high cellular uptake to final concentrations of 4.2 mM was observed upon incubation with 50 μM solutions of the Ruthenocene–PNA conjugate. The Ruthenocene label was shown to be an excellent label in all respec...

  • A Ruthenocene–PNA Bioconjugate — Synthesis, Characterization, Cytotoxicity, and AAS-Detected Cellular Uptake
    Bioconjugate Chemistry, 2012
    Co-Authors: Annika Gross, Nina Husken, Julia Schur, łukasz Raszeja, Nils Metzler-nolte
    Abstract:

    Labeling of peptide nucleic acids (PNA) with metallocene complexes is explored herein for the modulation of the analytical characteristics, as well as biological properties of PNA. The synthesis of the first Ruthenocene–PNA conjugate with a dodecamer, mixed-sequence PNA is described, and its properties are compared to a ferrocene-labeled analogue as well as an acetylated, metal-free derivative. The synthetic characteristics, chemical stability, analytical and thermodynamic properties, and the interaction with cDNA were investigated. Furthermore, the cytotoxicity of the PNA conjugates is determined on HeLa, HepG2, and PT45 cell lines. Finally, the cellular uptake of the metal-containing PNAs was quantified by high-resolution continuum source atomic absorption spectrometry (HR-CS AAS). An unexpectedly high cellular uptake to final concentrations of 4.2 mM was observed upon incubation with 50 μM solutions of the Ruthenocene–PNA conjugate. The Ruthenocene label was shown to be an excellent label in all respec...

Taekmo Chung - One of the best experts on this subject based on the ideXlab platform.

  • Ruthenocene precursors for ruthenium containing thin film deposition an example of solvent nucleophilic attack on fulvene
    Organometallics, 2017
    Co-Authors: Eun Ae Jung, Sheby Mary George, Bo Keun Park, Taekmo Chung
    Abstract:

    A new series of Ruthenocene complexes were prepared from RuCl3·xH2O and 6,6-dimethylfulvene as potential precursors for thin-film deposition. The formation of these complexes was the result of an unforeseen nucleophilic attack of the solvent molecules (alcohols/amines) on the 6,6-dimethylfulvene ligand during the reaction. Complexes [RuII(C5H4C(CH3)2OCH3)2] (1), [RuII(C5H4C(CH3)2OC2H5)2] (2), [RuII(C5H4C(CH3)2N(CH3)2)2] (3), and [RuII(C5H4C(CH3)2N(CH2CH3)2)2] (4) were isolated in pure form and characterized by Fourier transform (FT) infrared and FT nuclear magnetic resonance spectroscopy as well as elemental and thermogravimetric (TG) analyses. Crystallographic studies of complexes 1–3 revealed a monomeric Ruthenocene structure for all complexes and showed that the deprotonated alkylalkoxide or dialkylamide of the solvent molecule was attached to the exocyclic carbon of the fulvene ligand. Although the complexes were formed as Ruthenocenes instead of the expected ruthenium fulvene complexes, they all disp...

Masaru Sato - One of the best experts on this subject based on the ideXlab platform.

  • On the accuracy of density-functional methods for determining structures of dicationic binuclear Ruthenocene derivatives bridged by an unsaturated molecule
    Journal of Molecular Structure: THEOCHEM, 2020
    Co-Authors: Toshiyuki Takayanagi, Kenta Takahashi, Takashi Fujihara, Masaru Sato
    Abstract:

    [著者版]Various exchange and correlation functionals have been examined in density-functional calculations for obtaining reliable optimized structures for dicationic binuclear Ruthenocenes bridged by an unsaturated compound, which has a characteristic fulvene-type structure. First, we have performed extensive calculations for Ruthenocene (RuCp2) in D-5h symmetry. It has been found that the Ru-Cp optimized distance is linearly correlated with the energy difference between highest occupied a(1)' and e(2)' orbitals. We have then found that the optimized structure of dicationic binuclear Ruthenocenes is strongly dependent of the a(1)'-e(2)' orbital sequence observed in RuCp2. In particular, when exchange-correlation functionals giving the a(1)' < e(2)' orbital sequence are employed, the contribution of the fulvene-type structure is found to be significantly underestimated in the optimized structure of dicationic binuclear Ruthenocenes. We finally demonstrate that the SVWN exchange-correlation functionals give reasonable optimized structures comparable to experimental structures determined by X-ray crystallography analysis. (c) 2006 Elsevier B.V. All rights reserved

  • synthesis and some properties of binuclear Ruthenocene derivatives bridged by both ethene and thiophene derivatives
    Journal of Organometallic Chemistry, 2008
    Co-Authors: Masaru Sato, Tatsumi Kitamura, Tomohiro Masiko, Kei Unoura
    Abstract:

    Abstract Binuclear Ruthenocenes bridged by ethenes and thiophene derivatives, Rc–CH CH–Z–Rc and Rc ∗ –CH CH–Z–CH CH–Rc ∗ (Z = thiophene, thieno[3,2- b ]thiophene, and 2,2′-bithiophene; Rc = ruthenocenyl, R ∗  = 1′,2′,3′,4′,5′-pentamethylruthenocenyl) were prepared. These complexes showed a one-step two-electron redox wave in the cyclic voltammograms, in contrast to the benzenoid-bridged dinuclear Ruthenocenes. The chemical oxidation of the Rc–CH CH–Z–Rc complexes gave no stable oxidized species. The two-electron oxidized species of the Rc ∗ –CH CH–Z–CH CH–Rc ∗ complexes were comparably stable and contained a fulvene-complex type structure.

  • On the accuracy of density-functional methods for determining structures of dicationic binuclear Ruthenocene derivatives bridged by an unsaturated molecule
    Journal of Molecular Structure-theochem, 2007
    Co-Authors: Toshiyuki Takayanagi, Kenta Takahashi, Takashi Fujihara, Masaru Sato
    Abstract:

    Abstract Various exchange and correlation functionals have been examined in density-functional calculations for obtaining reliable optimized structures for dicationic binuclear Ruthenocenes bridged by an unsaturated compound, which has a characteristic fulvene-type structure. First, we have performed extensive calculations for Ruthenocene (RuCp2) in D5h symmetry. It has been found that the Ru–Cp optimized distance is linearly correlated with the energy difference between highest occupied a 1 ′ and e 2 ′ orbitals. We have then found that the optimized structure of dicationic binuclear Ruthenocenes is strongly dependent of the a 1 ′ – e 2 ′ orbital sequence observed in RuCp2. In particular, when exchange-correlation functionals giving the a 1 ′ e 2 ′ orbital sequence are employed, the contribution of the fulvene-type structure is found to be significantly underestimated in the optimized structure of dicationic binuclear Ruthenocenes. We finally demonstrate that the SVWN exchange-correlation functional give reasonable optimized structures comparable to experimental structures determined by X-ray crystallography analysis.

  • synthesis and redox behavior of Ruthenocene terminated oligoenes characteristic and stable two electron redox system and lower potential shift of the two electron oxidation wave with elongating conjugation
    Chemistry: A European Journal, 2004
    Co-Authors: Masaru Sato, Takashi Fujihara, Atsushi Tanemura, Toru Nagata, Shigekazu Kumakura, Kei Unoura
    Abstract:

    : Ruthenocene-terminated butadienes and hexatrienes were prepared by the Wittig reaction of 3-ruthenocenyl-2-propenals with ruthenocenylmethylphosphonium salts and the Mukaiyama coupling of the propenals, respectively. Cyclic voltammetry of these complexes indicated that they were involved in a stable two-electron redox process. The oxidation potentials for Ruthenocene-terminated oligoenes shifted progressively to lower potential with the increasing CH==CH units as follows: Rc--Rc (0.32 V)>RcCH==CHRc (+0.09 V)>Rc(CH==CH)(2)Rc (-0.06 V)>Rc(CH==CH)(3)Rc (-0.07 V), (Rc=Ruthenocene). The tendency is in remarkable contrast to that in the successive one-electron redox process. These complexes were chemically oxidized to give stable crystalline solids, whose structures were confirmed by NMR spectroscopy and X-ray analysis to be oligoene analogues of a bis(fulvene) complex, for example, [(eta(5)-C(5)Me(5))Ru[mu(2)-eta(6):eta(6)-C(5)H(4)CH(CH==CH)(n)CHC(5)H(4)]Ru(eta(5)-C(5)Me(5))](2+) (n=1 or 2). The DFT calculation of the two-electron-oxidized species reproduced well the fulvene-complex structure for the Ruthenocene moieties. Since both the neutral and oxidized species are stable and chemically reversible, this redox system may be serviceable as a two-electron version of the ferrocene one-electron redox system.

  • the synthesis and redox behaviors of binuclear Ruthenocene derivatives bridged by an aromatic moiety
    Journal of Organometallic Chemistry, 2002
    Co-Authors: Masaru Sato, Genta Maruyama, Atsushi Tanemura
    Abstract:

    Abstract 2-Ruthenocenyl-4,4,5,5-tetramethyl-1,3-dioxa-2-borolane was prepared by the boration and the subsequent reaction with dilithium pinacolate as the starting material of the Suzuki–Miyaura coupling reaction. The dioxaborolane was heated with 1,4-dibromobenzene, 1,2-diiodobenzene, 4,4′-dibromobiphenyl, 1,4-dibromonaphthalene, and 2,6-dibromonaphthalene in the presence of (dppf)PdCl 2 –aqueous NaOH in DME to give the corresponding bis(ruthenocenyl) derivatives in moderate yields. The reaction of the dioxaborolane with 2,2′-diiodobiphenyl and 1,8-diiodo-naphthalene in the presence of Pd(PPh 3 ) 4 –Cs 2 (CO) 3 in N , N -dimethylformamide (DMF) produced ruthenoceno[l]phenanthrene and ruthenocenyl[a]acenaphthylene in low yield, respectively. The result of the cyclic voltammetry suggests that there is weak electronic interaction between the two metal sites in the two-electron oxidized species of the binuclear Ruthenocene derivatives with an aromatic bridge.