- Detection and Structural Investigation of Elusive Palladium Hydride Intermediates Formed from Simple Metal Salts
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The Mizoroki-Heck reaction is one of the most known and best studied catalytic transformations and has provided an outstanding driving force for the development of catalysis and synthetic applications. Three out of four classical Mizoroki-Heck catalytic cycle intermediates contain Pd-C bonds and are well known and studied in detail. However, a simple palladium hydride (which is formed after the product-releasing β-H-elimination step) is a kind of elusive intermediate in the Mizoroki-Heck reaction. In the present study, we performed a combined theoretical and mass spectrometry (MS) study of palladium hydride complexes [PdX2H]- (X = Cl, Br, and I), which are reactive intermediates in the Mizoroki-Heck reaction. Static and molecular dynamic calculations revealed that these species have a T-shaped structure with a trans-arrangement of halogen atoms. Other isomers of [PdX2H]- are unstable and easily rearrange into the T-shaped form or decompose. These palladium hydride intermediates were detected by MS in precatalyst activation using NaBH4, Et3N, and a solvent molecule as reducing agents. Online MS monitoring allowed the detection of [PdX2H]- species in the course of the Mizoroki-Heck reaction.
- Kostyukovich, Alexander Yu.,Burykina, Julia V.,Eremin, Dmitry B.,Ananikov, Valentine P.
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p. 7128 - 7142
(2021/05/26)
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- Dynamic Kinetic Resolution of Alcohols by Enantioselective Silylation Enabled by Two Orthogonal Transition-Metal Catalysts
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A nonenzymatic dynamic kinetic resolution of acyclic and cyclic benzylic alcohols is reported. The approach merges rapid transition-metal-catalyzed alcohol racemization and enantioselective Cu-H-catalyzed dehydrogenative Si-O coupling of alcohols and hydrosilanes. The catalytic processes are orthogonal, and the racemization catalyst does not promote any background reactions such as the racemization of the silyl ether and its unselective formation. Often-used ruthenium half-sandwich complexes are not suitable but a bifunctional ruthenium pincer complex perfectly fulfills this purpose. By this, enantioselective silylation of racemic alcohol mixtures is achieved in high yields and with good levels of enantioselection.
- Oestreich, Martin,Seliger, Jan
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supporting information
p. 247 - 251
(2020/10/29)
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- Preparation and Reactivity of Mixed-Ligands Hydride Complexes [RuHCl(CO)(PPh3)2{P(OR)3}]
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Mixed-ligands hydride complexes [RuHCl(CO)(PPh3)2{P(OR)3}] (2) (R = Me, Et) were prepared by allowing [RuHCl(CO)(PPh3)3] (1) to react with an excess of phosphites P(OR)3 in refluxing benzene. Treatment of hydrides 2 first with triflic acid and next with an excess of hydrazine afforded hydrazine complexes [RuCl(CO)(κ1-NH2NHR1)(PPh3)2{P(OR)3}]BPh4 (3, 4) (R1 = H, CH3). Diethylcyanamide derivatives [RuCl(CO)(N≡CNEt2)(PPh3)2{P(OR)3}]BPh4 (5) were also prepared by reacting 2 first with HOTf and then with N≡CNEt2. The complexes were characterized spectroscopically and by X-ray crystal structure determination of [RuHCl(CO)(PPh3)2{P(OEt)3}] (2b).
- Albertin, Gabriele,Antoniutti, Stefano,Castro, Jesús
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p. 688 - 693
(2019/05/10)
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- Ionic Pd/NHC Catalytic System Enables Recoverable Homogeneous Catalysis: Mechanistic Study and Application in the Mizoroki–Heck Reaction
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N-Heterocyclic carbene (NHC) ligands are ubiquitously utilized in catalysis. A common catalyst design model assumes strong M–NHC binding in this metal–ligand framework. In contrast to this common assumption, we demonstrate here that lability and controlled cleavage of the M?NHC bond (rather than its stabilization) could be more important for high-performance catalysis at low catalyst concentrations. The present study reveals a dynamic stabilization mechanism with labile metal–NHC binding and [PdX3]?[NHC-R]+ ion pair formation. Access to reactive anionic palladium intermediates formed by dissociation of the NHC ligands and plausible stabilization of the molecular catalyst in solution by interaction with the [NHC-R]+ azolium ion is of particular importance for an efficient and recyclable catalyst. These ionic Pd/NHC complexes allowed for the first time the recycling of the complex in a well-defined form with isolation at each cycle. Computational investigation of the reaction mechanism confirms a facile formation of NHC-free anionic Pd in polar media through either Ph–NHC coupling or reversible H–NHC coupling. The present study formulates novel ideas for M/NHC catalyst design.
- Eremin, Dmitry B.,Denisova, Ekaterina A.,Yu. Kostyukovich, Alexander,Martens, Jonathan,Berden, Giel,Oomens, Jos,Khrustalev, Victor N.,Chernyshev, Victor M.,Ananikov, Valentine P.
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supporting information
(2019/11/14)
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- Palladium-Catalyzed Direct Intramolecular C-N Bond Formation: Access to Multisubstituted Dihydropyrroles
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A palladium-catalyzed intramolecular amination of alkenes with retention of olefin functionalization was achieved under mild reaction conditions. In the presence of palladium catalyst, the tosyl-protected amine can directly couple with a double bond to provide versatile dihydropyrrole derivatives in moderate to excellent yields.
- Jiang, Bing,Meng, Fei-Fan,Liang, Qiu-Ju,Xu, Yun-He,Loh, Teck-Peng
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supporting information
p. 914 - 917
(2017/02/26)
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- Urinary tract infection fighting potential of Newly synthesized ruthenium carbonyl complex of N-dehydroacetic acid-N′-o-vanillin-ethylenediamine
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In recent years, there has been a growing fascination towards the development of new antimicrobial agents from various sources to combat microbial resistance. Klebsiella pneumonia and E. coli are the main urinary tract infection (UTI) causing agents. Herein, we report the synthesis and characterization of a novel carbonyl complex of Ru(II) that has been found a good antimicrobial agent against the selected microbes. Hence, may be suggested as potent agent against UTI. The compound on characterization was found octahedral in structure on the basis of comparative DFT-experimental characterization. Molecular specification under B3LYP functional, LANL2DZ basis set for Ru atom and 6-31?g(d,p) for all other atoms were employed. Electron density plots and geometrical optimization were the main theoretical aspects that were invoked. Elemental analysis, mass spectrometry, NMR, FT-IR, UV–Vis and cyclic voltammetry were the physio-chemical techniques at both the experimental and theoretical fronts that helped to establish the proposed structure. From the overall study, it may be remarked that both observed and computed outcomes have been found in good agreement with each other.
- Mir,Jain,Malik,Chourasia,Vishwakarma,Rajak,Maurya
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- A Ruthenium Catalyst with Unprecedented Effectiveness for the Coupling Cyclization of - Amino Alcohols and Secondary Alcohols
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The ruthenium complex (8-(2-diphenylphosphinoethyl)aminotrihydroquinolinyl)(carbonyl)(hydrido)ruthenium chloride exhibited extremely high efficiency toward the coupling cyclization of -amino alcohols with secondary alcohols. The corresponding products, pyridine or quinoline derivatives, are obtained in good to high isolated yields. On comparison with literature catalysts whose noble-metal loading with respect to -amino alcohols reached 0.5-1.0 mol % for Ru and a record lowest of 0.04 mol % for Ir, the current catalyst achieves the same efficiency with a loading of 0.025 mol % for Ru. The mechanism of acceptorless dehydrogenative condensation (ADC) was proposed on the basis of DFT calculations; in addition, the reactive intermediates were determined by GC-MS, NMR, and single-crystal X-ray diffraction. The catalytic process is potentially suitable for industrial applications.
- Pan, Bing,Liu, Bo,Yue, Erlin,Liu, Qingbin,Yang, Xinzheng,Wang, Zheng,Sun, Wen-Hua
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p. 1247 - 1253
(2016/02/18)
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- PLANT BASED MONOMERS AND POLYMERS
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The preparation of cyclohexadienes from one or more plant oils is disclosed. The cyclohexadiene can be used to form polymers or derivatized to form other monomers that can be used to form polymeric materials.
- -
-
Paragraph 0029; 0061
(2014/01/07)
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- Ruthenium(II)-catalyzed regioselective reductive coupling of α-imino esters with dienes
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A method for the highly regioselective reductive coupling reaction of N-aryl-α-imino esters with dienes is described. The method utilizes the RuHCl(CO)(PPh3)3/iPrOH catalytic system under an Ar atmosphere and provides α-branched allylic α-amino acid derivatives. Application of this transformation to the concise synthesis of a natural plant growth regulator is demonstrated.
- Zhu, Shujie,Lu, Xiaoxia,Luo, Yueting,Zhang, Wei,Jiang, Huanfeng,Yan, Ming,Zeng, Wei
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supporting information
p. 1440 - 1443
(2013/06/27)
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- Hydrogenation of olefins over hydrido chlorocarbonyl tris-(triphenylphosphine) ruthenium(II) complex immobilized on functionalized MCM-41 and SBA-15
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Hydrido chlorocarbonyl tris-(triphenylphosphine) ruthenium(II) complex [RuHCl(CO)(PPh3)3] has been immobilized inside the pores of amine functionalized MCM-41 and SBA-15 materials. These grafted complexes were characterized by XRD, F
- Joseph, Trissa,Deshpande,Halligudi,Vinu,Ernst,Hartmann
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- The kinetic instability of σ-bound aryloxide in coordinatively unsaturated or labile complexes of ruthenium
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Reaction of RuCl2(PPh3)3 (1) or RuHCl(PPh3)3 (2) with KOAr (Ar=4-tBuC6H4) in non-alcohol solvents affords π-aryloxide derivatives Ru(η5-ArO)(o-C6H4PPh2) (PPh3) (3a) or RuH(η5-ArO)(PPh3) 2 (6a), respectively. The phenoxide analogues 3b and 6b are obtained on use of KOPh or TlOPh. Treatment of 1 with 1 equiv. KOAr in the presence of isopropanol liberates the phenol and acetone, affording clean 2 in quantitative yields. In 3:1 methanol-CH2Cl2, RuHCl(CO)(PPh3)3 (4) is also formed in small amounts. Reaction of 1 with 2 KOAr in 20% MeOH-CH2Cl2 affords a mixture of 6a and RuH2(CO)(PPh3)3 (5). In the corresponding reaction of 2 with 1 KOAr, σ-π isomerization of the σ-aryloxide ligand dominates, affording 6a·MeOH as the principal product. Treatment of 6a with ethereal HCl gives [RuH(η6-ArOH)(PPh3)2]Cl (7a); the corresponding reaction of 6b yields RuCl(η5-PhO)(PPh3)2 (8b). The crystal structures of 3a, 3b, 4, 5, 7a, and 8b are reported.
- Snelgrove,Conrad,Yap,Fogg
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p. 268 - 278
(2008/10/08)
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- Synthesis, spectral and electrochemical studies of ruthenium(II)/(III) complexes of alicyclic β-ketamines
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A series of ruthenium(II)/(III) complexes of alicyclic β-ketamines derived from 2-formylcyclohexanone and 4-X-substituted anilines, HFCA-X (where H is an ionisable enolic hydrogen and X = H, Cl, Br, OMe and NO2), have been prepared and characterized by spectroscopic techniques. The IR spectral data suggest the coordination of enolic oxygen and imino nitrogen to ruthenium. Ruthenium(II) complexes are diamagnetic (low spin d6, S = 0) and in solutions show intense MLCT transition. Their redox behaviours have been studied by cyclic voltammetry. The solid state low temperature ESR spectra of Ru(III) complexes show a low spin symmetry.
- Prasanna,Srinivasan,Rajagopal,Athappan
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p. 426 - 429
(2007/10/03)
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- Mechanisms of C-Si and C-H Bond Formation on the Reactions of Alkenylruthenium(II) Complexes with Hydrosilanes
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Reactions of the four alkenylruthenium(II) complexes Ru[C(R1)=CH(R2)]Cl(CO)(PPh3)2 (R1 = H, R2 = Ph (1b); R1 = H, R2 = t-Bu (1c); R1 = Ph, R2 = Ph (1d); R1 = CH=CH(SiMe3), R2 = SiMe2Ph (1e)) with HSiMe2Ph, which constitute the product-forming step of ruthenium-catalyzed hydrosilylation of alkynes, have been examined. Two reaction courses are operative: one provides the C-Si coupling product PhMe2SiC(R1)=CH(R2) and RuHCl(CO)-(PPh3)3 (path A), and the other forms the C-H coupling product HC(R1)=CH(R2) and Ru(SiMe2Ph)Cl(CO)(PPh3)2 (path B). The ratio of the two courses significantly varies with substituents on the alkenyl ligands, particularly with the α-substituent (R1). Thus, 1b and 1c, without an α-substituent, react mainly by path A. In contrast, 1d and 1e, bearing an α-substituent, exclusively undergo path B. Kinetic studies using 1b and its para-substituted styryl ligand derivatives have revealed that path A proceeds by direct interaction of the five-coordinated complexes with hydrosilane, without dissociation of the PPh3 ligand. On the other hand, path B involves dissociation of PPh3 prior to the reaction of 1d or 1e with hydrosilane. Mechanisms of the C-Si and C-H bond formation are discussed with kinetic data in detail.
- Maruyama, Yooichiroh,Yamamura, Kunihiro,Sagawa, Takashi,Katayama, Hiroyuki,Ozawa, Fumiyuki
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p. 1308 - 1318
(2008/10/08)
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- Mechanistic study of ruthenium-catalyzed hydrosilation of 1- (Trimethylsilyl)-1-buten-3-yne
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Catalytic hydrosilation of 1-(trimethylsilyl)-1-buten-3-yne (1) with three kinds of hydrosilanes (HSiMePh2, HSiMe2Ph, and HSiEt3) in CDCl3 at 30 °C in the presence of a catalytic amount of RuHCl(CO)(PPh3)3 (2) gave five types of reaction products: (1E,3E)-CH(SiR3)=CHCH=CHSiMe3 (3), R3SiCH2-CH=CHCH2SiMe3 (4), R3SiCH=C=CHCH2SiMe3 (5), (1Z,3E)- CH(SiR3)=CHCH=CHSiMe3 (6), and R3SiC≡CCH=CHSiMe3 (7). Detailed investigations on the stoichiometric reactions of intermediate ruthenium species provided definitive evidence for the catalytic mechanism comprised of two catalytic cycles, the Chalk-Harrod cycle A and the modified Chalk-Harrod cycle C, and their interconnecting processes B and D. Product 3 is formed by the insertion of 1 into the Ru-H bond of 2 followed by the reaction of the resulting terminal dienyl complex Ru(CH=CHCH=CHSiMe3)Cl(CO)(PPh3)2 (8) with hydrosilane. The latter process regenerates 2 and the sequence of reactions proceeds catalytically (cycle A). The reaction of 8 with hydrosilane is accompanied by a side reaction giving Ru(SiR3)Cl(CO)(PPh3)2 (9) and CH2=CHCH=CHSiMe3 (10), and the latter is further converted to 4 by hydrosilation (process B). Silyl complex 9 thus generated in the system is the key intermediate for catalytic cycle C. Thus the insertion of 1 into the Ru-SiR3 bond of 9 via a formal trans-addition process forms an internal dienylruthenium complex Ru[C(CHSiR3)CH=CHSiMe3]Cl(CO)-(PPh3)2 (11), which reacts with hydrosilane to give 5 and 6 and to regenerate 9. A part of 11 also undergoes β-hydrogen elimination to give a dehydrogenative silation product 8 and hydride complex 2. Complex 2 thus formed resumes catalytic cycle A (process D). The catalytic intermediates 8, 9, and 11 were identified by NMR spectroscopy and/or elemental analysis. Factors controlling the catalytic cycles are discussed on the basis of the experimental observations.
- Maruyama, Yooichiroh,Yamamura, Kunihiro,Nakayama, Isao,Yoshiuchi, Keigo,Ozawa, Fumiyuki
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p. 1421 - 1429
(2007/10/03)
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- Some organometallic chemistry of ruthenium(II)
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Stoichiometric and catalytic reactions of Ru(II) phosphine complexes with alkynes, olefins, and enynes are described.The hydride complex RuCl(CO)H(PPh3)3 (1) reacts with the double bond of a cis-enyne whereas it reacts with triple bonds of trans-enynes.Metathesis of vinyl silanes with olefins are catalyzed by 1 where β-Si elimination is the key step.Dimerizations of t-Bu- and Me3Si-substituted acetylenes into the corresponding butatrienes are catalyzed by Ru(II) active species as studied by isolation of the intermediates.A model reaction for the crucial step of the catalytic cycle, formation of a Ru vinylidene complex from acetylene, has been fully simulated by ab initio-MO calculations.Keywords: Ruthenium; Olefins; Alkynes; Catalysis; Crystal structure; MO calculations
- Wakatsuki, Yasuo,Yamazaki, Hiroshi
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p. 349 - 362
(2007/10/02)
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- SYNTHESIS OF SOME BINUCLEAR RUTHENIUM(ii) COMPLEXES INVOLVING CHEMICALLYNON-EQUIVALENT RUTHENIUM(II) CENTRES
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Binuclear ruthenium(II) complexes of the type [(PPh3)2(CO)HRu-cdc-Ru(Cp)(Eph3)2] have synthesized, where E = P, As and cdc is a polyfunctional bridging ligand N=C-N=CS2(2-).
- Pandeya, K. B.,Pandey, D. S.,Tripathi, I. P.,Agrawala, U. C.
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p. 663 - 670
(2008/10/09)
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- Metal Complexes of Biologically Important Ligands, LXX. - Synthesis, Stereochemistry and Reactions of Ruthenium(II) and Osmium(II) Complexes with α-Amino Carboxylates
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The reactions of MHCl(CO)(PPh3)3 with salts of α-amino acids give the hydrido-N,O-chelate complexes MH(CO)(NH2CHRCOO)(PPh3)2 (1a-g; M = Ru, Os).Complexes 1a-c can alternatively be prepared by oxidative addition of the appropriate α-amino acid to Ru(CO)3(PPh3)2.The crystal structure of 1b has been determined by an X-ray structural analysis.The leucinato compound 1c is an effective catalyst for the decomposition of formic acid.In contrast, reactions of RuHCl(CO)(PPh3)3 with α-amino acids afford the chloro-N,O-chelate complexes RuCl(CO)(NH2CHRCOO)(PPh3)2 2a-h.The decomposition reactions of 2c, 2g and 2h have been investigated. - Key Words: Ruthenium complexes / Osmium complex / Hydrido complexes / α-Amino acids / Oxidative Addition
- Severin, Kay,Suenkel, Karlheinz,Beck, Wolfgang
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p. 615 - 620
(2007/10/02)
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- Half-way coordination state of a butadienyl group on ruthenium. η3-Allylic bonding with η1-character or vice versa.
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The butadienyl complexes formed by the reaction of trans-(R1)CH=CHCCR2 (R1, R2=SiMe3, t-Bu, Me, Et) with RuCl(CO)H(PPh3)3 exhibit unique structures: instead of taking the 18-electron configuration of the metal by conventional η3-coordination of the butadienyl ligand, they shift significantly to the 16-electron η1-coordination state.
- Wakatsuki, Yasuo,Yamazaki, Hiroshi,Maruyama, Yooichiroh
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p. C60 - C63
(2007/10/02)
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- Ruthenium-catalysed Disproportionation between Vinylsilanes and Mono-substituted Alkenes via Silyl Group Transfer
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Selective cross-disproportion between vinylsilanes and various mono-substituted alkenes is catalysed by 1; the mechanism of this reaction has been elucidated based on reactions of 1 with vinylsilanes as well as those of the resulting ruthenium-silyl complex with alkenes.
- Wakatsuki, Yasuo,Yamazaki, Hiroshi,Nakano, Masato,Yamamoto, Yasuhiro
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p. 703 - 704
(2007/10/02)
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- Phenylacetylene dimerization promoted by ruthenium(II) complexes
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The complex Ru(CO)(CH=CHPh)Cl(C5H5N)(PPh3)2 and related alkenyl complexes react in methanol or ethanol to give (E,E)-1,4-diphenylbuta-1,3-diene and the ruthenium(II) hydride Ru(CO)H(Cl)(C5H5N)(PPh3)3.Futher reaction of this hydride with the butadiene results in 1,2-reduction to yield (E)-1,4-diphenyl-1-butene.However, the reaction of phenylacetylene with catalytic amounts of ruthenium hydrides gave the dimer (Z)-1,4-diphenylbuten-3-yne.On the other hand, the reaction of 1,2-diphenylethenylruthenium(II) derivatives in methanol or ethanol gave trans-stilbene rather than the butadiene.Several deuteration experiments were performed in order to elucidate the mechanism of formation of (E,E)-1,4-diphenylbuta-1,3-diene and ruthenium hydride from the corresponding alkenyl complexes.
- Echavarren, Antonio M.,Lopez, Javier,Santos, Amelia,Montoya, Julio
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p. 393 - 400
(2007/10/02)
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- Synthesis and catalytic activity of heterodinuclear Ru-Ir and Ru-Rh Complexes. Crystal structure of (pz = pyrazolate, TFB = tetrafluorobenzobarrelene)
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Reactions of the ruthenium compounds (R = Ph, n = 3; R = iPr, n = 2) with pyrazole C3H4N2 (Hpz) give the complexes .Treatment of these complexes with a hydrogen abstractor (methoxide ion or acetylacetonate (acac)), such as 2 (M = Ir, Rh; diolefin = cycloocta-1,5-diene (COD), tetrafluorobenzobarrelene (TFB) or 3-C3H5)> has given the heterobinuclear complexes (R = Ph; M = Ir or Rh, L2 = COD or TFB; R = iPr, M = Rh, L2 = TFB; R = Ph, M = Pd, L2 = C3H5).The structure of has been established by an X-ray diffraction study.The species is binuclear, with a pyrazolate group and chlorine atom as bridging ligands.The intermetallic separation is 3.8907(6) Angstroem.The reduction of cyclohexanone by hydrogen transfer from isopropanol catalyzed by (H(CO)(PPh3)2Ru(μ-Cl)(μ-pz)M(diolefin)> (M = Ir, Rh; diolefin = COD, TFB) is also reported.
- Garcia, Maria P.,Lopez, Ana M.,Esteruelas, Miguel A.,Lahoz, Fernando J.,Oro, Luis A.
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p. 365 - 377
(2007/10/02)
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- THE RUTHENIUM-CATALYSED CONVERSION OF METHANOL INTO METHYL FORMATE
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Heating of methanol with yields methyl formate and hydrogen, together with some dimethoxymethane; at the end of the reaction much of the catalyst is present as the dinuclear cation, +.
- Smith, Thomas A.,Aplin, Richard P.,Maitlis, Peter M.
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p. C13 - C14
(2007/10/02)
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- COMBINED DECARBOXYLATION OF THE FORMATO LIGAND AND REDUCTIVE ELIMINATION OF HYDRIDO AND ARYL GROUPS IN THE SYNTHESIS OF RUTHENIUM(0) COMPLEXES. METHYLATION OF RUTHENIUM(0) WITH FORMALDEHYDE
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The formato ligand is readily introduced into the 5-coordinate complexes MRCl(CO)(PPh3)2 (M = Ru or Os, R = o-tolyl) giving 6-coordinate MR(η2-O2CH)(CO)(PPh3)2.In the presence of excess PPh3 thermal decarboxylation of the osmium complex leads to the stable aryl, hydride, OsRH(CO)(PPh3)3.A similar reaction with RuR(η2-O2CH)(CO)(PPh3)2 is accompanied by reductive elimination of RH and formation of Ru(CO)(PPh3)3 which as a solid is ortho-metallated, i.e. exists as .Decarboxylation and reductive elimination in the presence of bis(diphenylphosphino)ethane (dppe) give the zerovalent Ru(CO)(dppe)2. Ru(CO)(PPh3)3 undergoes a most unusual reaction with formaldehyde forming Ru(CH3)(η2-O2CH)(CO)(PPh3)2.
- Roper, W.R.,Wright, L.J.
-
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- PREPARATION OF OCTAHEDRAL, HYDRIDO-AQUO-RUTHENIUM(II) COMPLEXES, AND STRUCTURAL CHARACTERISATION OF HYDRIDOAQUODICARBONYLBIS(TRIPHENYLPHOSPHINE)RUTHENIUM(II) TETRAFLUOROBORATE
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Reaction of RuH2(CO)(PPh3)3 with tetrafluoroboric acid/water gives BF4.Carbonylation of the latter compound yields BF.In the Ir spectra of these compounds, splitting of the asymmetric BF4- stretching band indicated the possibility of a coordinated tetrafluoroborato ligand, but an X-ray study of BF4 shows that the BF4- is not coordinated to the metal, but is involved in a network of hydrogen bonds with the coordinated water molecule and the ethanol molecule of crystallisation.The crystal are monoclinic, space group P21 with Z = 2 in a unit cell of dimensions a = 9.3959(4), b = 22.695(1), c = 9.7878(3) Angstroem, β - 109.12(1) deg.The observed and calculated densities are 1.39 and 1.404 g cm-3 respectively.The structure was solved by conventional methods and refined using the full-matrix least-squares equations to final residuals R and Rw of 0.048 and 0.064 respectively.The ruthenium atom is in a distorted octahedral coordination geometry.The Ru-CO distances (1.83 and 1.97(2) Angstroem) differ significantly, with the longer bond situated trans to the hydrido ligand.The Ru-P bonds (2.329 and 2.416(5) Angstroem) are also significantly different, and the P-Ru-P angle is markedly non-linear at 165.1(2) deg.This asymmetry can be attributed to crystal packing forces.
- Boniface, Suzanne M.,Clark, George R.,Collins, Terrence J.,Roper, Warren R.
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p. 109 - 117
(2007/10/02)
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