cas 1287-13-4, BIS(CYCLOPENTADIENYL)RUTHENIUM

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One-electron oxidation of ruthenocene: Reactions of the ruthenocenium ion in gentle electrolyte media
The electrochemical oxidation of ruthenocene, RuCp2 (Cp = η5-C5H5), 1, has been studied in dichloromethane using a supporting electrolyte containing either the [B(C 6F5)4]-
Swarts, Jannie C.,Nafady, Ayman,Roudebush, John H.,Trupia, Sabrina,Geiger, William E.
p. 2156 - 2165
(2009)
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1H-NMR spectroscopic studies of anion and solvent effects on mixed-valence iodobiruthenocenium(II, IV) salts
Oxidation of 1,1''-biruthenocene with iodoruthenocenium(IV)+Y- salts in CH2Cl2 gives iodo-1,1''-biruthenocenium(II,IV)+Y- salts (Y = PF6, BF4, 2,4,6-(NO2)3C6H2O, CCl3COO * CCl3COOH).The electron exchange reaction between RuII and RuIV with iodide, migration was investigated by temperature-dependent 1H-NMR spectroscopy in CD3COCD3 and the mixed-solvent solutions CDCl3-CD3COCD3, CDCl3-CD3CN and CCl4-CD3COCD3 with a range of mixing ratios.The activation energy of the reaction increases as the concentration of low dielectric constant solvent increases.
Watanabe, Masanobu,Iwamoto, Toschitake,Sano, Hirotoshi,Motoyama, Izumi
p. 197 - 202
(1993)
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A New Synthetic Method for the Preparation of Cyclo-olefin Ruthenium Complexes
Hydrated ruthenium trichloride reacts with cyclohexa-1,3-diene and cyclo-octa-1,5-diene, in the presence of metallic zinc, to give the ruthenium(0) compounds 1-6-η-benzene(1-4-η-cyclohexa-1,3-diene)ruthenium, (1), and (1-2:5-6-η-cyclo-octa-1,5-diene)(1-6-η-cyclo-octa-1,3,5-triene)ruthenium, (2), respectively.The analogous reaction with cyclo-octa-1,3-diene, cyclohepta-1,3-diene, and cyclopentadiene leads to the isolation of the corresponding dienyl complexes bis(1-5-η-cyclo-octadienyl)ruthenium, (3), bis(1-5-η-cycloheptadienyl)-ruthenium, (4), and ruthenocene, (5).Complex (3) is best prepared by heating (2) in hydrocarbon solvents at ca. 100 deg C.
Pertici, Paolo,Vitulli, Giovanni,Paci, Maurizio,Porri, Lido
p. 1961 - 1964
(1980)
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Microwave-Assisted Synthesis and Transformations of Cationic CpRu(II)(naphthalene) and CpRu(II)(naphthoquinone) Complexes
Details of the direct synthesis of cationic Ru(II)(η5-Cp)(η6-arene) complexes from ruthenocene using microwave heating are reported. Developed for the important catalyst precursor [Ru(II)(η5-Cp)(η6-1-4,4a,8a-naphthalene)][PF6] reaction time could be shortened from three days to 15 min. The method was extended to [Ru(II)(η6-benzene)(η5-Cp)][PF6], [Ru(II)(η5-Cp)(η6-toluene)][PF6], [Ru(II)(η5-Cp)(η6-mesitylene)][PF6], [Ru(II)(η5-Cp)(η6-hexamethylbenzene)][PF6], [Ru(II)(η5Cp)(η6-indane)][PF6], [Ru(II)(η5-Cp)(η6-2,6-dimethylnaphthalene)][PF6], and [Ru(II)(η5-Cp)(η6-pyrene)][PF6]. 1-methylnaphthalene and 2,3-dimethylnaphthalene afforded mixtures of regioisomeric complexes. [Ru(Cp)(CH3CN)3][PF6], derived from the naphthalene precursor provided access to the cationic RuCp complexes of naphthoquinone, tetralindione, 1,4-dihydroxynaphthalene, and 1,4-dimethoxynaphthalene. Reduction of the tetralindione complex afforded selectively the endo,endo diol derivative. X-Ray structures of five complexes are reported.
Bocekova-Gajdo?íkova, Eva,Epik, Bugra,Chou, Jingyu,Akiyama, Katsuhiro,Fukui, Nobuaki,Guénée, Laure,Kündig, E. Peter
(2019)
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Moessbauer Spectroscopic Studies of Tin(IV) Halide Adducts with Ruthenocene and with Ferrocenophanes
Adducts of tin(IV) halide with ferrocenophane were prepared by treating SnX4 (X=Cl or Br) with ferrocenophane in hexane.The adducts were studied by means of 57Fe- and 119Sn-Moessbauer spectroscopy and other physicochemical measurements.Anomalously large quadrupole splittings (3.49 mm s-1 for ferrocenophane-1.5SnCl4 adduct and 3.47 mm s-1 for ferrocenophane-1.5SnBr4 adduct, both at 78 degK) found in the 57Fe-Moessbauer spectroscopy and organotin(IV) species (e.g., isomer shift value, 2.14 mm s-1 for the ferrocenophane-1.5SnCl4 adduct and 2.10mm s-1 for the ferrocenophane-1.5SnBr4 adduct, both at 78 degK) found from the 119Sn-Moessbauer spectroscopy suggest that a direct chemical bonding between Fe and Sn atoms is formed in the ferrocenophane adducts, as the Ru-Sn bonding in the ruthenocene-1.5SnCl4 adduct (isomer shift value, 2.08 mm s-1 at 78 degK).
Watanabe, Masanobu,Motoyama, Izumi,Sano, Hirotoshi
p. 2109 - 2114
(1986)
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Site-Specific Deoxyfluorination of Small Peptides with [18F]Fluoride
Radiolabeled receptor-binding peptides are an important class of positron emission tomography tracers owing to achievable high binding affinities and their rapid blood clearance. Herein, a method to introduce a 4-[18F]fluoro-phenylalanine residue into peptide sequences is reported, by chemoselective radio-deoxyfluorination of a tyrosine residue using a traceless activating group. The replacement of only one hydrogen atom with [18F]fluoride results in minimal structural perturbation of the peptide, which is desirable in the labeling of tracer candidates.
Rickmeier, Jens,Ritter, Tobias
p. 14207 - 14211
(2018)
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CYCLOPENTADIENYL-RUTHENIUM AND -OSMIUM COMPLEXES III. CHEMICAL MECHANISM OF DISSOLUTION OF CHLORO(η-CYCLOPENTADIENYL)-BIS(TRIPHENYLPHOSPHINE)RUTHENIUM(II) IN POLAR SOLVENTS
The conversion of CpRuCl(PPh3)2 in boiling ethylene glycol within 90 h of reflux has been investigated.New complex cations in the form of their tetraphenylborates, for which the formulae 1RuCl(PPh3)PPh2Cp2Ru(η-C6H5)>+ and + are proposed, were isolated.The former cation is also formed at lower temperatures during the reflux of CpRuCl(PPh3)2 in methanol.The following process takes place: 2CpRuCl(PPh3)2 -> 1RuCl(PPh3)PPh2Cp2Ru(η-C6H5)>+ + Cl- + 2PPh3.In the presence of dicyclopentadiene during the reflux of CpRuCl(PPh3)2 in high boiling polar solvents (ethylene glycol, dimethyl sulphoxide), ruthenocene is formed in a 90 percent yield.One of the cyclopentadienyl groups in ruthenocene originates from dicyclopentadiene.As a result of the reaction of CpRuCl(PPh3)2 and NaBPh4 in a mixture of diglyme and methanol, a colourless, crystalline compound, CpRu(η-C6H5)BPh3, is obtained in a 50-60 percent yield.
Wilczewski, Tadeusz
p. 331 - 340
(1985)
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New method for the synthesis of substituted ruthenocenes
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Karslyan,Konovalov,Perekalin,Petrovskii,Kudinov
p. 2032 - 2033
(2008)
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A convenient synthetic route to [CpRu(CH3CN3)]PF6
A convenient synthetic route to [CpRu(CH3CN)3]PF6 was presented. A new practical protocol that avoids the stoichiometric use of either thallium or silver salts for the synthesis of the given compound was described. It was shown that the introduction of the cyclopentadienyl ligand via ethanolic reduction of [(arene)RuCl2]2 in the presence of cyclopentadiene is a simple and convenient entry to cyclopentadienylruthenium complexes.
Trost, Barry M.,Older, Christina M.
p. 2544 - 2546
(2002)
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Mixed-Valent Ruthenocene-Vinylruthenium Conjugates: Valence Delocalization Despite Chemically Different Redox Sites
Ruthenocene-vinylruthenium conjugates Rc/Rc-CHa?CH-Ru(CO)(L)(PiPr3)2 (Rc = (??5-C5H5)Ru(??5-C5H4); Rc? = (??5-C5Me5)Ru(??5-C5H4); L = Cl or ?°O,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, ?"E1/2, in the ruthenocene congeners. All experimental results are backed by quantum chemical calculations.
Hassenrück, Christopher,Mang, André,Winter, Rainer F.
p. 2695 - 2707
(2019)
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IMPROVED METHOD FOR SYNTHESIS OF ARENECYCLOPENTADIENYLRUTHENIUM CATIONS
An improved method for the synthesis of + salts by means of ligand exchange at ruthenocene is described.A set of new +X- was obtained.The 1H NMR spectra of arenecyclopentadienylruthenium salts were discussed.
Vol'kenau, N. A.,Bolesova, I. N.,Shul'pina, L. S.,Kitaigorodskii, A. N.,Kravtsov, D. N.
p. 341 - 348
(1985)
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A new mechanistic path in the reaction of ruthenium trichloride with silylated cyclopentadienes. Ionic transition metal halides as desilylating agents
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Winter,Pirzad,Cao
p. 1026 - 1027
(1991)
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Organometallic nucleoside analogues: Effect of the metallocene metal atom on cancer cell line toxicity
A new chiral organometallic nucleoside analogue containing ruthenocene is reported, in which alkylthymine and alkylhydroxyl groups are attached in adjacent positions on one cyclopentadienyl ring. The synthetic procedures for this metallocene derivative and two control compounds are described, along with their characterisation by cyclic voltammetry and X-ray crystallography. Their biological activities in a human pancreatic cancer cell line (MIA-Pa-Ca-2) were significantly lower than those of three previously reported analogous ferrocene compounds, indicating that the choice of metallocene metal atom (Fe or Ru) plays a pivotal role in determining the anticancer properties of these nucleoside analogues, which in turn suggests a different mode of action from that of a conventional nucleoside analogue.
Ismail, Media K.,Armstrong, Katie A.,Hodder, Samantha L.,Horswell, Sarah L.,Male, Louise,Nguyen, Huy V.,Wilkinson, Edward A.,Hodges, Nikolas J.,Tucker, James H. R.
p. 1181 - 1190
(2020)
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CYCLOPENTADIENYL-RUTHENIUM AND -OSMIUM COMPLEXES V. SYNTHESIS, REACTIVITY AND CRYSTAL STRUCTURE DETERMINATION OF CARBONYLCHLORO(η-CYCLOPENTADIENYL)-(TRIPHENYLPHOSPHINE)RUTHENIUM(II)
CpRuCl(CO)PPh3 is formed as the result of refluxing CpRuCl(PPh3)2 in ethylene glycol (yield up to 15percent).A dissociation process is postulated with liberation of one PPh3 molecule and simultaneous rearrangement of the cation formed earlier: +Cl- -> CpRuCl(CO)PPh3 + PPh3.CpRuCl(CO)PPh3 reacts reluctantly with the alkoxy anion to give CpRuH(PPh3), in contrast to CpRuCl(PPh3)2, which undergoes very facile transformation into CpRuH(PPh3)2.The structure of CpRuCl(CO)PPh3 has been determined by the single-crystal X-ray diffraction method.The compound is triclinic, space group P, a 9.378(2), b 10.584(2), c 16.590(4) Angstroem, α 126.11(1), β 55.91(1), γ 101.49(1) deg .The unit cell contains both R and S enantiomers.A shorter distance of the Ru-Cl bond has been noted in CpRuCl(CO)PPh3 (2.396 Angstroem) in comparison with the Ru-Cl distance in CpRuCl(PPh3)2 (2.453 Angstroem).This causes a diminishing tendency to lose a chloride ion and as a result, nucleophilic attack of RO- on CpRuCl(CO)PPh3.
Wilczewski. Tadeusz,Dauter, Zbigniew
p. 349 - 356
(1986)
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MOLECULAR QUADRUPOLE MOMENTS, MAGNETIC ANISOTROPIES, AND CHARGE DISTRIBUTIONS OF FERROCENE AND RUTHENOCENE.
Measurements of the infinite-dilution molar Kerr constants, field-gradient birefringence constants, and Cotton-Mouton constants of ferrocene and ruthenocene as solutes in cyclohexane at 25 degree C are reported. The observations yield the effective polarizability anisotropy, the electric quadrupole moment, and the magnetic anisotropy of each molecule. Analysis of these properties shows that ferrocene and ruthenocene are more polarizable in directions parallel, rather than perpendicular, to the ligand-metal-ligand axes; it suggests that the bonding results in transfer of electronic charge from the metal atom toward the cyclopentadienyl rings; and it enables the observed magnetic anisotropies to be separated into oppositely signed diamagnetic and temperature-independent paramagnetic contributions. A useful new synthesis of ruthenocene is described.
Ritchie,Cooper,Calvert,Dennis,Phillips,Vrbancich
p. 5151 - 5219
(1983)
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Synthesis, Computational Studies, Inelastic Neutron Scattering, Infrared and Raman Spectroscopy of Ruthenocene
In this work we report a new and simplified synthesis of ruthenocene that prevents the formation of unwanted by-products. We have also revisited the vibrational spectroscopy of this iconic molecule and in addition to infrared and variable temperature Raman spectra, we present the first inelastic neutron scattering (INS) spectrum, a technique that is little used in inorganic chemistry. The Raman spectra in the low energy range (–1) clearly show that the mode assigned as the ring–Ru–ring torsion is a librational mode. By generating the INS spectra predicted by previous assignment schemes we are able to show that they are all, at least partially, wrong because they fail to correctly predict the experimental INS spectrum. In the case of ruthenocene, the addition of INS data, in combination with periodic-DFT calculations, has enabled the first correct assignment of the internal modes of ruthenocene. This straightforward means to test proposed assignments is one of the great strengths of vibrational spectroscopy with neutrons.
Parker, Stewart F.,Butler, Ian R.
p. 1142 - 1146
(2019)
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NEW HIGH YIELD SYNTHESES OF RUTHENOCENE AND OSMOCENE AND THEIR DECAMETHYL DERIVATIVES. THE CRYSTAL STRUCTURE OF 5-C5Me5)2>
Reaction of x> (x > 2; cod = cycloocta-1,5-diene) with SnBu3(C5R5) (R= H, Me) gives 5-C5R5)2> (M= Ru, R= H, Me; M= Os, R= H) and 5-C5Me5)H(cod)>.Decamethylosmocene, 5-C5Me5)2>, has been
Liles, David C.,Shaver, Alan,Singleton, Eric,Wiege, Manfred B.
p. C33 - C36
(1985)
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Synthesis, reactivity, and characterization of ruthenocenes bearing pentazincated cyclopentadienyl ligands
Treatment of pentakis(chloromercurio)pentamethylruthenocene or decakis(chloromercurio)ruthenocene with dimethylzinc affords ruthenocenes containing pentazincated cyclopentadienyl ligands. The reactivity of the perzincated ruthenocenes is presented, along
Seneviratne, Kapila N.,Winter, Charles H.
p. 2498 - 2499
(1997)
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Octadienediyl Dichlorides of Ruthenium (IV) as Synthetic Reagents in Organoruthenium Chemistry; Isolation of a Protonated 'Open Metallocene' 5-C7H11)2H>
Chloride extraction from 3:ν3-C10H16)Cl2L> tNCl>, in the presence of diolefins, results in labilisation of the 2,7-dimethyloctadienediyl ligand and provides syntheses of some new organoruthenium complexes, including the protonated 'open metallocene' 5-C7H11)2H>.
Cox, David N.,Roulet, Raymond
p. 951 - 953
(1988)
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Eisen- und Ruthenium-Komplexe mit 1,1-Difluoroethen
1,1-Difluorethylene reacts with CpFe(CO)2CH3 (1) and CpRu(CO)2CH3 (2) yielding the two new complexes CpFe(CO)(COCH3)CFCH (3) and CpRu(CO)2CH2CF3 (4).The formation of 3 and 4 underlines the ease of HF elimination of fluoroolefines in the presence of transi
Keim, Wilhelm,Fischer, Wolfgang
p. C20 - C23
(1991)
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Reduction of ruthenium arenecyclopentadienyl complexes reactions induced by electron transfer
Ruthenium arenecyclopentadienyl complexes [Ru(η5-C5R5)(η6-arene)]+ (1, R = H, arene = C6H6; 2, R = Me, arene = C6H6; 3, R = H; arene = C6H3
Gusev, Oleg V.,Ievlev, Mikhail A.,Peterleitner, Mikhail G.,Peregudova, Svetlana M.,Denisovich, Larisa I.,Petrovskii, Pavel V.,Ustynyuk, Nikolai A.
p. 57 - 66
(1997)
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REAGENT AND PROCESS FOR THE SITE-SPECIFIC DEOXYFLUORINATION OF PEPTIDES
The present invention refers to reagents and methods for preparing a peptide sequence having a [18F]fluoro-aromatic amino acid side which may be further substituted, in particular a 4-[18F]fluoro-phenylalanine side chain in peptide sequences, by chemoselective radio-deoxyfluorination of an aromatic amino acid residue, in particular a tyrosine residue using a traceless-activating group and the reagents used in said process.
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Page/Page column 13

(2020/01/31)

Synthesis and some properties of binuclear ruthenocene derivatives bridged by both ethene and thiophene derivatives
Binuclear ruthenocenes bridged by ethenes and thiophene derivatives, Rc-CH{double bond, long}CH-Z-Rc and Rc*-CH{double bond, long}CH-Z-CH{double bond, long}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{double bond, long}CH-Z-Rc complexes gave no stable oxidized species. The two-electron oxidized species of the Rc*-CH{double bond, long}CH-Z-CH{double bond, long}CH-Rc* complexes were comparably stable and contained a fulvene-complex type structure.
Sato, Masaru,Kitamura, Tatsumi,Masiko, Tomohiro,Unoura, Kei
p. 247 - 256
(2008/03/14)

Method for preparing bis(cyclopentadienly)ruthenium and bis(cyclopentadienyl)ruthenium prepared by the method
The present invention provides a method of manufacturing a bis(cyclopentadienyl)ruthenium, comprising the step of synthesizing a bis(cyclopentadienyl)ruthenium by causing cyclopentadiene, ruthenium chloride and zinc powder to react in an alcohol solvent, wherein the synthesis of the bis(cyclopentadienyl)ruthenium comprises the step of mixing the cyclopentadiene and zinc powder in the alcohol solvent and thereafter adding ruthenium chloride portionwise while holding the temperature of the reaction system at from ?70° C. to 20° C. A highly pure product can be obtained through purification of subliming bis(cyclopentadienyl)ruthenium having been synthesized in the synthesis step in an atmosphere under reduced pressure.
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(2008/06/13)

Synthesis of bis (cyclopentadienyl) and bis (indenyl) ruthenium complexes
A process for preparing a cyclopentadienyl or indenyl ruthenium complex by treatment of a cyclopentadienyl or indenyl compound with ruthenium trichloride dihydrate and magnesium powder in an alkanol at 10° C. to ?30° C. is described.
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(2008/06/13)

Synthesis of bis (cyclopentadienyl) and bis (indenyl) ruthenium complexes
A process for preparing a cyclopentadienyl or indenyl ruthenium complex by treatment of a cyclopentadienyl or indenyl compound with ruthenium trichloride dihydrate and magnesium powder in an alkanol at 10° C. to ?30° C. is described.
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(2008/06/13)

The synthesis and redox behaviors of binuclear ruthenocene derivatives bridged by an aromatic moiety
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)PdCl2-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(PPh3)4-Cs2(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.
Sato, Masaru,Maruyama, Genta,Tanemura, Atsushi
p. 23 - 30
(2007/10/03)

Pharmaceuticals providing diagnosis and selective tissue necrosis using Mossbauer absorber atom
Pharmaceuticals and Apparatus used in combination for diagnosis and tissue necrosis applicable to provide effective and selective therapy using the Mossbauer absorption phenomenon. Selected pharmaceutical compounds containing a radiation absorber isotope are administered to a tissue and excited by a radiation source which provides energy at the corresponding resonant Mossbauer absorption frequency of isotope containing pharmaceutical, where excitation effects nuclear transitions to cause highly selective energy absorption in the selected target tissue. For diagnostic purposes, de-excitation fluorescence of the isotope is monitored. For therapeutic purposes, the energy is converted to particle radiation by the isotope at the target tissue by internal conversion followed by an Auger electron cascade which results in radiolysis of DNA resulting in lethal double strand breaks in the DNA molecules of the target tissue.
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(2008/06/13)

Multiple ligand transfer reaction between [CpRu(L)(AN)2][PF6] (L = AN, CO, P(OMe)3; AN = acetonitrile) and CpFe(CO)L′X (L′ = CO, PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X = Cl, Br, I)
Treatment of ruthenium complexes [CpRu(AN)3][PF6] (1a) (AN = acetonitrile) with iron complexes CpFe(CO)2X (2a-2c) (X = Cl, Br, I) and CpFe(CO)L′X (6a-6g) (L′ = PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X = Cl, Br, I) in refluxing CH2Cl2 for 3 h results in a triple ligand transfer reaction from iron to ruthenium to give stable ruthenium complexes CpRu(CO)2X (3a-3c) (X = Cl, Br, I) and CpRu(CO)L′X (7a-7g) (L′ = PMe3, PMe2Ph, PMePh2, PPh3, P(OPh)3; X = Br, I), respectively. Similar reaction of [CpRu(L)(AN)2][PF6] (1b: L = CO, 1c: P(OMe)3) causes double ligand transfer to yield complexes 3a-3c and 7a-7h. Halide on iron, CO on iron or ruthenium, and two acetonitrile ligands on ruthenium are essential for the present ligand transfer reaction. The dinuclear ruthenium complex 11a [CpRu(CO)(μ-I)]2 was isolated from the reaction of 1a with 6a at 0°C. Complex 11a slowly decomposes in CH2Cl2 at room temperature to give 3a, and transforms into 7a by the reaction with PMe3.
Katayama, Taku,Onitsuka, Kiyotaka,Takahashi, Shigetoshi
p. 31 - 37
(2007/10/03)

Efficient synthesis of ruthenium(II) η5-dienyl compounds starting from Di-μ-chlorodichloro-bis[(1-3η:6-8η)-2,7-dimethyloctadienediyl] diruthenium(IV). Versatile precursors for enantioselective hydrogenation catalysts
The dimeric complex di-μ-chlorodichloro-bis[(1-3η:6-8η)-2,7-dimethyloctadienediyl] diruthenium(IV) in the presence of base reacts with cyclic and acyclic dienes to the corresponding bis(η5-dienyl)ruthenium(II) compounds. Crystalline yellow comp
Bauer, André
p. 5471 - 5476
(2008/10/08)

Electronic effects on the rates of coupled two-electron/halide self-exchange reactions of substituted ruthenocenes
The complexes (Me(m)Cp)(Me(n)Cp)Ru (m,n = 1,1; 0,4; 0,5; 1,5) have been synthesized along with the corresponding halometalloceniums [(Me(m)Cp)(Me(n)Cp)RuX]+ (X = Cl, Br, I). The two-electron/halide transfer self-exchange kinetics have been dete
Shea, Timothy M.,Westmoreland, T. David
p. 1573 - 1577
(2008/10/08)

Improvements in the preparation of cyclopentadienyl thallium and methylcyclopentadienylthallium and in their use in organometallic chemistry
Improved preparation methods of cyclopentadienylthallium and methylcyclopentadienylthallium, giving quantitative yields and incorporating ultrasound techniques, are described. Their use as starting materials for a wide range of organometallic syntheses is discussed and demonstrated.
Neto, Alberto Federman,Borges, Aurea Donizete Lanchote,Miller, Joseph,Darin, Vitor Andre
p. 1299 - 1314
(2008/10/09)

Pentamethylpentalithioruthenocene and decalithioruthenocene
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Bretschneider-Hurley, Annette,Winter, Charles H.
p. 6468 - 6469
(2008/10/08)

Multiple desilylation of silylated cyclopentadienes promoted by ionic ruthenium and rhodium halides
The reactivity of hydrated ruthenium trichloride and hydrated rhodium trichloride toward silylated cyclopentadienes was investigated. Treatment of ruthenium trichloride with (trimethylsilyl)cyclopentadiene, bis(trimethylsilyl)cyclopentadiene, or tris(trimethylsilyl)cyclopentadiene in alcohol solvents afforded ruthenocene in 85-96% isolated yields. GLC analysis of these reactions, as well as the reactions of benzyltriethylammonium chloride with (trimethylsilyl)cyclopentadiene, bis(trimethylsilyl)cyclopentadiene, and tris(trimethylsilyl)cyclopentadiene, revealed a novel chloride ion-induced desilylation of the silylated cyclopentadienes. These experiments demonstrated that the silylated cyclopentadienes were completely desilylated by chloride ion to afford cyclopentadiene, which then reacted with the ruthenium ion to afford ruthenocene. Treatment of hydrated rhodium trichloride with (trimethylsilyl)cyclopentadiene or cyclopentadiene monomer afforded cyclopentadienylrhodium dichloride oligomer in 93% and 82% yields, respectively. Treatment of hydrated rhodium trichloride with bis(trimethylsilyl)cyclopentadiene afforded cyclopentadienylrhodium dichloride oligomer (27%) and (trimethylsilyl)cyclopentadienylrhodium dichloride dimer (70%). The structure of (trimethylsilyl)cyclopentadienylrhodium dichloride dimer was determined, showing that this compound crystallized in the triclinic space group P1 with cell dimensions a = 10.797(6) ?, b = 11.204(4) ?, c = 11.335(3) ?, α = 79.23(2)°, β = 70.28(3)°, γ = 64.75(3)°, V = 1166.0(8) ?3, and Z = 2.
Winter, Charles H.,Pirzad, Shahin,Graf, David D.,Cao, Danh H.,Heeg, Mary Jane
p. 3654 - 3659
(2008/10/08)

Chemistry of cyclopentadienyl-ruthenium and -osmium complexes. 1. The preparation and substitution reactions of (η4-cycloocta-1,5-diene)(η 5-cyclopentadienyl)haloruthenium(II) complexes. Versatile new synthetic precursors to open-face cyclopentadienyl-ruthenium(II) chemistry
Treatment of [(η4-C8H12)RuH(NH2NMe 2)3]PF6 (C8H12 = cycloocta-1,5-diene) with cyclopentadienylthallium in refluxing acetone affords the novel cyclopentadienyl-ruthenium(II) complex [η5-C5H5)Ru(η4-C 8H12)H] (1). Reaction of 1 with halogenating agents (CCl4, CH2Br2, CH3I) in pentane gives the halo complexes [(η5-C5H5)Ru(η4-C 8H12)X] (2-4; X = Cl, Br, I), while halide metathesis on 2 using either NaBr or NaI in methanol provides alternative routes to 3 and 4, respectively. The substitution of the cycloocta-1,5-diene and/or chloro ligands in 2 in a range of solvents and under mild reaction conditions is a rapid and facile process. Mono- and bidentate ligands [CO, PPh3, PMe3, 1,2-bis(diphenylphosphino)ethane, P(OMe)3, PPh2H, MeNC, t-BuNC, 2,6-Me2C6H3NC, CN(CH2)6NC, 3,4,7,8-Me4-1,10-phenanthroline] and the dienes (buta-1,3-diene, 2,3-dimethylbuta-1,3-diene, 1-methyl-4-(methoxycarbonyl)buta-1,3-diene, bicyclo[2.2.1]hepta-2,5-diene) substitute the cycloocta-1,5-diene ligand in 2, in ethanol, acetone, or tetrahydrofuran solutions to give neutral products of the general type [(η5-C5H5)RuL2Cl]. Polyolefins (cyclohepta-1,3,5-triene, cycloocta-1,3,5-triene, cyclooctatetraene) and aromatics (benzene, hexamethylbenzene, indene, benzyl chloride, triphenylamine) react with 2 in refluxing ethanol solution to give, following anion exchange with NH4PF6, salts of the general formulation [(η5-C5H5)RuL3]PF6. Sodium tetraphenylborate reacts directly with 2 in refluxing ethanol to give the zwitterionic η6-arene complex [(η6-C5H5)Ru(η6-C 6H5BPh3)]. Cyclopentadienylsodium reacts with 2 in tetrahydrofuran at room temperature giving ruthenocene, while sodium hydrotris(1-pyrazolyl)borate (NaHBpz3) with 2 in ethanol yields the unusual metallocene [(η5-C5H5)Ru(HBpz3)]. These compounds are all obtained in high yield and have been characterized by a combination of elemental analysis and spectroscopic methods (IR and 1H and 13C NMR spectroscopy).
Albers, Michel O.,Robinson, David J.,Shaver, Alan,Singleton, Eric
p. 2199 - 2205
(2008/10/08)

Chemistry of cyclopentadienyl-ruthenium and -osmium complexes. 3. New high-yield syntheses of ruthenocenes and osmocenes. The crystal and molecular structures of decamethylruthenocene [Ru(η5-C5Me5)2] and decamethylosmocene [Os(η5-C5Me5)2]
The reaction of [{Ru(η4-C8H12)Cl2}x] (C8H12 = cycloocta-1,5-diene) with cyclopentadienylthallium in dimethoxyethane gives [Ru(η5-C5H5)2] (1) in 78% yield. A generalized route from [{Ru(η4-C8H12)Cl2}x] and [Sn-n-Bu3(C5R5)] (R = H, Me) in ethanol at 80°C gives 1 and [Ru(η5-C5Me5)2] (2) (yields 75% and 70%, respectively). Correspondingly [{Os(η4-C8H12)Cl2}x] reacts with [Sn-n-Bu3(C5H5)] in methanol at 65°C to afford [Os(η5-C5H5)2] (3) in 72% yield. Decamethylosmocene, [Os(η5-C5Me5)2] (4), is obtained in 82% yield by the direct reaction between pentamethylcyclopentadiene and Na2[OsCl6] in ethanol. Mixed-ligand ruthenocenes, [Ru(η5-C5H5)(η5-C 5H4Me)] (5) and [Ru(η5-C5H5) (η5-C5Me5)] (6), are obtained by the treatment of the labile ruthenium(II)-cyclopentadienyl complex [(η5-C5H5)Ru(η4-C 8H12)Cl] with the appropriate cyclopentadienyl anions (C5H4Me-, C5Me5-) in tetrahydrofuran at 25°C. The reactions of [M(η5-C5Me5)2] (M = Ru, Os) with halogens X2 (X = Br, I) give the ruthenium(IV) and osmium(IV) cations [M(η5-C5Me5)2X]Y (M = Ru, X, Y = Br, 7; M = Ru, X = I, Y = I3, 8; M = Os, X, Y = Br, 9; M = Os, X = I, Y = I3, 10). Strong acids reversibly protonate the electron-rich centers in 2 and 4 giving the cationic hydride complexes [M(η5-C5Me5)2H]+. The complexes 1-10 have been characterized by elemental analysis and by spectroscopic (IR and 1H and 13C NMR) techniques. The crystal and molecular structures of 2 and 4 have been determined by single-crystal X-ray diffraction. Crystals of these sandwich complexes are isostructural, space group P21/n. Abnormally high thermal parameters indicate the presence of disorder across the mirror plane. Although the position of the molecules across the crystallographic mirror plane implies a D5h (eclipsed) molecular geometry in both cases, this may only reflect the average structure. The average metal-carbon distances are 2.17 (1) and 2.18 (1) A? for Ru-C and Os-C, respectively; d(C-C) = 1.43 (1) A? and d(C-C(Me)) = 1.52 (1) A?. In both structures there is a slight bending of the methyl groups (approximately 0.07 A?) away from the mean plane through the cyclopentadienyl ring.
Albers, Michel O.,Liles, David C.,Robinson, David J.,Shaver, Alan,Singleton, Eric,Wiege, Manfred B.,Boeyens, Jan C. A.,Levendis, Demetrius C.
p. 2321 - 2327
(2008/10/08)

THE PREPARATION AND SOME REACTIONS OF CHLORO(η4-CYCLOOCTA-1,5-DIENE)(η5-CYCLOPENTYDIENYL)RUTHENIUM(II) A VERSATILE, NEW SYNTHETIC PRECURSOR FOR CYCLOPENTADIENYLRUTHENIUM(II) CHEMISTRY
Facile substitution of the cyclooctadiene and/or chloro ligands in 5-C5H5)Ru(C8H12Cl)> (C8H12=cycloocta-1,5-diene) under mild reaction conditions provides high yield synthetic routes to a range of new neutral and cationic cyclopentadienylruthenium(II) complexes.
Albers, Michel O.,Oosthuizen, Hester E.,Robinson, David J.,Shaver, Alan,Singleton, Eric
p. C49 - C52
(2007/10/02)

Reactivity of haloruthenocene(IV) complexes
The ruthenium(IV)-containing compounds [Ru(cp)2Br]PF6 and [Ru(cp)2Cl]PF6 react with H2O, yielding ruthenocene and ring-oxidation products, Ru(cp)(cpO)Br and Ru(cp)(cpO)Cl, respectively. The structure of the oxidized bromo compound has been determined from 564 unique x-ray reflections. The compound crystallizes in the orthorhombic space group Pnma with unit cell dimensions a = 13.588 (2) ?, b = 8.876 (1) ?, c = 7.495 (1) ?, V = 904 (1) ?3, and Z = 4. The discrepancy indices are R1 = 3.05% and R2 = 3.51%. A mirror plane, containing the ruthenium and bromine atoms, bisects the cyclopentadienyl and cyclopentadienone (cpO) rings. The rings are in a staggered conformation and are bent away from the halide.
Smith, Terrance P.,Kwan, Keh Shin,Taube, Henry,Bino, Avi,Cohen, Shmuel
p. 1943 - 1945
(2008/10/08)

CYCLOPENTADIENYL-RUTHENIUM COMPLEXES. 1 THE REACTIVITY OF SOME ?-CYCLOPENTADIENYL-BISTRIPHENYLPHOSPHINE-RUTHENIUM(II) COMPLEXES
Several ruthenium complexes of the CpRuX(PPh3)2 type, where X=Cl, Br, I, NCS, NCO, CN, BH4, H, D, and some of the CpRuS2CZ(PPh3) type, where Z=NR2 or OR, were obtained.The hydride CpRuH(PPh3)2 was obtained in high yield by reaction of CpRuCl(PPh3)2 with R
Wilczewski, Tadeusz,Bochenska, Maria,Biernat, Jan F.
p. 87 - 96
(2007/10/02)