84821-53-4Relevant articles and documents
Carbon-sulfur bond cleavage in CpRu(η5-thiophene)+ and subsequent reactions of the butadiene-thiolate product
Hachgenei, Johannes W.,Angelici, Robert J.
, p. 359 - 378 (1988)
The complexes CpRu(η5-Th)+ (1), where Th is thiophene or a methyl-substituted thiophene, react with hydrides such as H2Al(OCH2CH2OMe)2- to give (eq.3) the C-S cleaved butadiene-thiolate product 3.Subsequent reactions of 3 are shown: This scheme is not intended to indicate that all reactions were performed on the thiophene complex; many were carried out using the methyl-substituted thiophene analogs.Structures of complexes of the types 6 and 9 were established by X-ray diffraction studies.Possible mechanisms for reaction 3 are considered, and stereochemistries of all complexes are established by 1 H NMR spectrometry.Implications for the mechanism of the catalytic hydrodesulfurization of thiophene are discussed.
Synthesis of the first 30-electron triple-decker complexes of the iron group metals with cyclopentadienyl ligands. X-Ray structure of PF6
Kudinov, A.R.,Rybinskaya, M.I.,Struchkov, Yu.T.,Yanovskii, A.I.,Petrovskii, P.V.
, p. 187 - 198 (1987)
The first 30-electron triple-decker complexes of the iron group metals PF6 were synthesized by reaction of PF6 or PF6 (R=H, Me) with decamethylmetallocenes M'(η-C5Me5)2 (M'=Fe, Ru, Os
SYNTHESIS AND CRYSTAL STRUCTURE OF NONAMETHYLRUTHENOCENYLCARBENIUM HEXAFLUOROPHOSPHATE
Kreindlin, A. Z.,Petrovskii, P. V.,Rybinskaya, M. I.,Yanovskii, A. I.,Struchkov, Yu. T.
, p. 229 - 238 (1987)
The hitherto unknown functional derivatives of decamethylruthenocene (I), viz. (C5Me5)RuC5Me4CHO (II), and C5Me5RuC5Me4CH2OH (III) have been synthesized.The interaction of III with acids results in C5Me5RuC5Me4CH2(+) X(-) (IV, X = BF4, PF6) which contain
Dehydrogenative Coupling of 4-Substituted Pyridines Catalyzed by a Trinuclear Complex of Ruthenium and Cobalt
Nagaoka, Masahiro,Kawashima, Takashi,Suzuki, Hiroharu,Takao, Toshiro
, p. 2348 - 2360 (2016/08/02)
The dehydrogenative coupling of 4-substituted pyridines catalyzed by a heterometallic trinuclear complex composed of Ru and Co, (Cp?Ru)2(Cp?Co)(μ-H)3(μ3-H) (1, Cp? = η5-C5Me5), was investigated. When the pyridine substrate contains an electron-donating group at the 4-position, complex 1 showed a high catalytic activity compared to di- and triruthenium complexes (Cp?Ru)2(μ-H)4 (4) and (Cp?Ru)3(μ-H)3(μ3-H)2 (5). The catalytic activity of 1 was also remarkably higher than the congeners of other group 9 metals, Ru2Rh (2) and Ru2Ir analogues (3). The distinctive reactivity of 1 was attributed to a paramagnetic intermediate, (Cp?Ru)2{(dmbpy)Co}(μ-H)(μ3-H)2 (12, dmbpy = 4,4′-dimethyl-2,2′-bipyridine), which was formed by the reaction of 1 with 4-picoline accompanied by the dissociation of the Cp? at the Co atom. The reaction of 12 with unsubstituted pyridine resulted in the elimination of 4,4′-dimethyl-2,2′-bipyridine, indicating that the Co atom in 12 acts as a dissociation site. In contrast to the reaction of 1 with 4-picoline, the reaction of 2 and 3 with 4-picoline afforded the corresponding μ3-pyridyl complexes (Cp?Ru)2(Cp?M)(μ-H)3(μ3-η2(||)-C5H3NCH3) (15, M = Rh; 16, M = Ir). 4-(Trifluoromethyl)pyridine was not dimerized by 1; however, a similar μ3-pyridyl complex, (Cp?Ru)2(Cp?Co)(μ-H)3(μ3-η2(||)-C5H3NCF3) (13), was obtained. The stability of the μ3-pyridyl complex is probably one of the reasons for the low catalytic activity of 2 and 3 in the coupling reaction.
PROCESS FOR PREPARING DIENYL-RUTHENIUM COMPLEXES
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Page/Page column 5, (2011/08/06)
The present invention relates to a single-stage process for preparing dienyl-ruthenium complexes of the formula Ru(+II)(dienyl)2, wherein an Ru(II) starting compound of the formula Ru(X)p(Y)q is reacted with a diene ligand in the presence of an inorganic and/or organic base in a single-stage process. Here, polar organic solvents, preferably mixtures of polar organic solvents with water, are used. The dienyl-ruthenium complexes prepared according to the invention are used as precursors for homo-geneous catalysts, for producing functional coatings and for therapeutic applications.
PROCESS FOR PREPARING DIENYL-RUTHENIUM COMPLEXES
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Page/Page column 14, (2009/12/28)
The present invention relates to a single-stage process for preparing dienyl- ruthenium complexes of the formula Ru(+II)(dienyl)2, wherein an Ru(II) starting compound of the formula Ru(X)p(Y)q is reacted with a diene ligand in the presence of an inorganic and/or organic base in a single-stage process. Here, polar organic solvents, preferably mixtures of polar organic solvents with water, are used. The dienyl-ruthenium complexes prepared according to the invention are used as precursors for homogeneous catalysts, for producing functional coatings and for therapeutic applications.
Comparative study of the reactivity of (Cp*RuCl)4 and (Cp*RuCl2)2 with trimethylsilyl-substituted oxodienyl ligands
Sanchez-Castro, M. Esther,Paz-Sandoval, M. Angeles
, p. 6071 - 6082 (2009/03/12)
A comparative study of the chemical reactivity of the well-known precursors [Cp*RuCl]4 (1) and [Cp*RuCl2]2 (2) is established relative to the incorporation of silyl-substituted heterodienyl compounds. This study gives clear evidence of the influence of the solvents and the oxidation state of 1 versus 2 on these reactions. In THF, tetramer 1 reacts selectively with CH2CHCHCHOSiMe3 (3) to afford [Cp*Ru(η4-CH2CHCHCHOSiMe3)Cl] (4), while the reaction of dimer 2 leads to nonselective reactions with the formation of 4 and [Cp*Ruη3-CH2CHCHCHO)Cl2] (5). Compound 5 is thermodynamically more stable than 4. The reactivity of 1 and the mixture of isomers CH2C(Me)CHC(OSiMe3)Me (6a) and MeC(Me)CHC(OSiMe3)CH2 (6b) affords oxo- and pentadienyl compounds [Cp*Ru{η5-CH2C(Me)CHC-(OSiMe 3)CH2}] (7), [Cp*Ru(η5-CH 2C(Me)CHC(Me)O] (8), and [Cp*Ru{η3-exo-syn- CH2C(Me)CHC-(Me)O]Cl2] (9). The treatment of 2 with 3 in methanolic or ethanolic solutions at room temperature provided a preparative route to the corresponding (allyl)ruthenium(IV) species: 5, [Cp*Ru{η3-endo-CH(Me)CHCHOR]Cl2] [R = Me (10); R = Et (12)]; [Cp*Ru{η3-endo-CH2CHCHCH(OR) 2}Cl2] [R = Me (11); R = Et (13)]. The ratio of the species formed could change significatively depending on the ratios of reactants or reaction conditions. The acetal derivatives 10-13 are generated as the result of nucleophilic attack of the alcohols on compound 5. When zinc is used as a reducing agent in ethanol, compound 2 reacts with 3 or the mixture of 6a and 6b to give trimetallic compounds Cp*Ru[η5-CH 2C(R)CHC(R)O]2(μ2-ZnCl2) (R = H, 14; R = Me, 15), which have a ZnCl2 bridging two Cp*Ru[η5-CH2C(R)CHC(R)O] molecules through the oxygen atoms of die corresponding oxopentadienyl ligands, along with [Cp*Ru{η4-CH2C(R)CHC(R)X}Cl] [R = H, X = OEt, 17; R = Me, X = OH, 18] as minor products. 15 reacts in the presence of CDCl3 to give the oxidative addition products exo-syn-9 and [Cp*Ru{η3-endo-anti-CH2C(Me)CHC(Me)O}Cl 2] (19). All compounds have been fully characterized by 1H and 13C NMR spectroscopy, and the crystal structures of 5, 9, 12, and 15 are also described.
Insertion reactions of GaCp*, InCp* and In[C(SiMe 3)3] into the Ru-Cl bonds of [(p-cymene)Ru IICl2]2 and [Cp*RuIICl] 4
Cokoja, Mirza,Gemel, Christian,Steinke, Tobias,Schroeder, Felicitas,Fischer, Roland A.
, p. 44 - 54 (2007/10/03)
The first carbonyl free ruthenium/low valent Group 13 organyl complexes are presented, obtained by insertion of ER (ER = GaCp*, InCp*, In[C(SiMe3)3]) into the Ru-Cl bonds of [(p-cymene)RuCl2]2, [Cp*RuCl]4 and [Cp*RuCl2]2. The compound [(p-cymene)RuCl 2]2 reacts with GaCp*, giving a variety of isolated products depending on the reaction conditions. The Ru-Ru dimers [{(p-cymene)Ru}2(GaCp*)4(μ3-Cl) 2] (1) and the intermediate [{(p-cymene)Ru}2(μ-Cl) 2] (2) were isolated, as well as monomeric complexes [(p-cymene)Ru(GaCp*)3Cl2] (3), [(p-cymene)Ru(GaCp*)2GaCl3] (4) and [(p-cymene)Ru(GaCp*)2Cl2(DMSO)] (5). The reaction of [Cp*RuCl]4 with ER gives piano-stool complexes of the type [Cp*Ru(ER)3Cl] (ER = InCp* (6), In[C(SiMe3)3] (7), GaCp* (8)). The chloride ligand in complex 8 can be removed by NaBPh4, yielding [Cp*Ru(GaCp*)3]+[BPh4]- (9). The reaction of [Cp*RuCl2]2 with GaCp* however, does not lead to an insertion product, but to the ionic Ru(II) complex [Cp*Ru(GaCp*)3]+[Cp*GaCl 3]- (10). The ER ligands in complexes 3, 5, 6, 7 and 8 are equivalent on the NMR timescale in solution due to a chloride exchange between the three Group 13 atoms even at low temperatures. The solid state structures, however, exhibit a different structural pattern. The chloride ligands exhibit two coordination modes: either terminal or bridging. The new compounds are fully characterized including single crystal X-ray diffraction. These results point out the different reactivities of the two precursors and the nature of the neutral p-cymene and the anionic Cp* ligand when bonding to a Ru(II) centre.
Syntheses, structures, and reactivity studies of half-open ruthenocenes and their oxodienyl analogues
Navarro Clemente, M. Elena,Saavedra, Patricia Juárez,Vásquez, Marisol Cervantes,Angeles Paz-Sandoval,Arif, Atta M.,Ernst, Richard D.
, p. 592 - 605 (2008/10/08)
Improved synthetic routes to Cp*Ru(Pdl) complexes (Pdl = 2,4-dimethylpentadienyl and various oxodienyl ligands) including Cp*Ru(η5-2,4-Me2-C4 H3O) (1), Cp*Ru[η5-2,4-(t-Bu)2-C4 H3O] (1'), and Cp*ru(η5-2,4-Me2-C5 H5) (1″) were developed. When chelating, diphosphines were used as coligands and reactions with O2, Cl2 or H2 led to oxidative addition. A carbon-carbon bond activation was reported.
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
Bauer, André
, p. 5471 - 5476 (2008/10/08)
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
