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The complex [RuCl(eta5-C5H5){PPh2(2-MeC 6H4)}2] (1), unlike the triphenylphosphine analog [RuCl(eta5-C5H5)(PPh3) 2], reacts under mild conditions with CO, N2CPh2 and HC?CPh to give the neutral carbonyl, carbene and vinylidene derivatives [RuCl(eta5-C5H5)(L){PPh 2(2-MeC6H4)}] (L = CO 2, CPh2 5, C=CHPh 6), respectively, via displacement of one phosphine ligand. The vinylidene complex 6 promptly reacts with benzylamine affording the aminocarbene [RuCl(eta5-C5H5){=C(NHCH 2Ph)CH2Ph} {PPh2(2-MeC6H4)}] (7). Moreover, the cyclometalated derivative [Ru(eta5-C5H5){PPh2(2-CH 2C6H4)}{PPh2(2-MeC6H 4)}] (4) has been obtained from the methyl complex [RuMe(eta5-C5H5){PPh2(2-MeC 6H4)}2] (3) by intramolecular C-H bond cleavage and methane elimination. Complex 1, whose X-ray structure analysis is also reported, has been found to catalyze alkyne coupling reactions.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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The activity of chloro(eta5-cyclopentadienyl)(didentate phosphine)ruthenium(II) complexes in the catalysis of two types of reaction with allylic alcohols is described. The isomerisation of 3-buten-2-ol to butanone (MEK) and allyl alcohol to propanal proceeds at high rates. A trend in catalytic activity is observed upon variation of the carbon-chain length in the didentate phosphine ligand: dppm < dppe < dppp < dppb. Complexes with rigid didentate phosphine ligands like cis-dppv and dppph show no activity. The second type of reaction constitutes the first example of a ruthenium-catalysed ether formation directly from allylic alcohols. Homo-coupled ethers like di-allyl ether (DAE) are easily formed as well as ethers from heterocoupling of allyl alcohol with aromatic and aliphatic alcohols. In fact, the ruthenium complexes achieve much higher turnover frequencies and turnover numbers than reported before in palladium-catalysed ether formation. Complexes with dppe and dppp in the presence of a conjugated diene switch from isomerisation to ether formation, but the new complex [RuClCp(o-MeO-dppe)] (Cp = eta5-cyclopentadienyl) (3) has proven to be very active in ether formation, even in the absence of a diene. The mechanisms of the reactions have been studied by using both deuterium-labelled substrates and 31P nuclear magnetic resonance (NMR). (C) 2000 Elsevier Science B.V. If you are interested in 32993-05-8, you can contact me at any time and look forward to more communication.Electric Literature of 32993-05-8

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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The water-soluble ruthenium(II) complexes Na2[RuCpX-(mTPPMS) 2] [X = Cl (1), I (2)] and Nax[RuCp(mTPPMS)(PR 13)-(PR23)](OTf)y [PR13 = PR23 = PPh3 (3), PTA (4), x = y = 0; PR13 = mTPPMS, PR2 3 = PTA (5), x = 1, y = 0; PR13 = mTPPMS, PR23 = mPTA (6), x = y = 0; PR13 = PR23 = mTPPMS (7), x = 2, y = 0; PR1 3 = PPh3, PR23 = PTA (8), x = y = 0; PR13 = mPTA, PR23 = PPh3 (9), x = 0, y = 1; mTPPMS = Ph2P(3-OSO2C 6H4)-; PTA = 1,3,5-triaza-7-phosphaadamantane; mPTA = N-methyl-1,3,5-triaza-7-phosphaadamantane] have been synthesized and characterised by elemental analysis, NMR and IR spectroscopy and crystallographic methods. The X-ray crystal structure determination of [RuCp(mTPPMS)(PPh3)-(PTA)]·2H2O (8·2H 2O), which is the first half-sandwich ruthenium complex bearing three different phosphanes, has also been determined. The binding properties of these new water-soluble ruthenium complexes towards DNA and the interaction of free mTPPMS with the nucleic acid have been studied using the mobility shift assay, which has shown that both the activity of the ruthenium complexes and the possible mechanism governing the interaction with DNA are strictly dependent on the composition of the complexes. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Ionic organometallic ruthenium(II) complexes, [eta5-CpRu(PPh3) (1,10-phenanthroline)]+Cl? 1, [eta5-CpRu(PPh3) (4,7-dimethyl, 1,10-phenanthroline)]+Cl? 2, and [eta5-CpRu(PPh3) (1,10-phenanthroline-5-amine)]+Cl? 3 have been synthesized and characterized. The molecular structures of the complexes 1 and 2 were confirmed by single-crystal X-ray structure analysis. Cytotoxicity assays demonstrated that these compounds show significant toxicity against NIH3T3 and Raw 264 cancer cell lines at low concentration. These complexes have the property of DNA binding cleavage.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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In this paper we report the reaction of [Ru(eta5-C5H5)Cl(PPh3)2] with P{CH2N(CH2CH2)2O}3 in the presence of NaBF4, in which, apart from the Cl- substitution, an unexpected P-C bond cleavage in the tertiary phosphane is observed. It results in the formation of [Ru(eta5-C5H5)(PH{CH2N(CH2CH2)2O}2)(PPh3)2]BF4 (1) – the first “piano-stool” ruthenium complex with a secondary aminomethylphosphane ligand.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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The reaction of buta-l,3-diyne with [RuUhfXPPhjJjOi-CjHj)](thf = tetrahydrofuran) to give [Ru(C=C=C=CH2)(PPh3)2(T)-CjHj)]+ has been studied. This complex adds nucleophiles at Cr, as expected from theory and consideration of the protection afforded to Ca by the bulky PPhj ligands. The products were alkenylethynyl complexes (from aprotic nucleophiles) or methylallenylidene complexes (from protic nucleophiles, with H migration to C6). With water, the complex [RufC^CQOJMeKPPhjJjOi-CsHj)] is formed. The single-crystal structures of [Ru{OC=CMe(X)}(PPh3)2(r|-CjHi)][PF6] (X = NPh2 or C4H3NMe-2) and [Ru(OCCH=CHCl-f/w)(PPhj)j(r|-CjH5)] have been determined.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
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Ligand substitution of [(Ind)Ru(PPh3)2Cl] (1) led to the isolation of [(Ind)Ru(PPh3)(Ph2P(CH2) 2C9H7}Cl] (2), [(Ind)Ru(dppf)Cl] (3) and [(Ind)Ru{(Ph2PCH2)3CMe}]PF6 ([4]PF6), and diastereoisomers [(R)- and (S)-(Ind)Ru(Josiphos)Cl] [(R)-5 and (S)-5], where (R)-(S)-Josiphos is the ferrocene-based chiral diphosphane ligand (R)-(-)-1-[(S)-2-(diphenylphosphanyl)ferrocenyl] ethyldicyclohexylphosphane. The Cp analogues of 5, viz. (R)-6 and (S)-6, were also obtained from [CpRu(PPh3)2Cl] (1a). Josiphos-dependent epimerisation was observed, with conversion of the (S) isomer to the (R) isomer in both cases. Chloride abstraction of 3 with NaPF 6 in CH3CN and NaN3 in EtOH gave [(Ind)Ru(dppf)(CH3CN)]PF6 ([7]PF6) and [(Ind)Ru(dppf)(N3)] (8), respectively. The azido ligand in 8 underwent [3+2] dipolar cycloaddition with dimethyl acetylenedicarboxylate to give a N-bound bis-(methoxycarbonyl)-1,2,3-triazolato complex, 9. X-ray crystal structures of the new complexes, except (R)-5, (S)-5 and (S)-6, have been determined. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
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Reactions of 3,6-bis(2-pyridyl)-4-phenylpyridazine (Lph) with [(eta6-arene)Ru(mu-Cl)Cl]2 (arene = C6H6, p-iPrC6H4Me and C6Me6), [(eta5-C5Me5)M(mu-Cl)Cl]2, (M = Rh and Ir) and [(eta5-Cp)Ru(PPh3)2Cl] (Cp = C5H5, C5Me5 and C9H7) afford mononuclear complexes of the type [(eta6-arene)Ru(Lph)Cl]PF6, [(eta5-C5Me5)M(Lph)Cl]PF6 and [(Cp)Ru(Lph)(PPh3)]PF6 with different structural motifs depending on the pi-acidity of the ligand, electronic properties of the central metal atom and nature of the co-ligands. Complexes [(eta6-C6H6)Ru(Lph)Cl]PF6 1, [(eta6-p-iPrC6H4Me)Ru(Lph)Cl]PF6 2, [(eta5-C5Me5)Ir(Lph)Cl]PF6 5, [(eta5-Cp)Ru(PPh3)(Lph)]PF6, (Cp = C5H5, 6; C5Me5, 7; C9H7, 8) show the type-A binding mode (see text), while complexes [(eta6-C6Me6)Ru(Lph)Cl]PF6 3 and [(eta5-C5Me5)Rh(Lph)Cl]PF6 4 show the type-B binding mode (see text). These differences reflect the more electron-rich character of the [(eta6-C6Me6)Ru(mu-Cl)Cl]2 and [(eta5-C5Me5)Rh(mu-Cl)Cl]2 complexes compared to the other starting precursor complexes. Binding modes of the ligand Lph are determined by 1H NMR spectroscopy, single-crystal X-ray analysis as well as evidence obtained from the solid-state structures and corroborated by density functional theory calculations. From the systems studied here, it is concluded that the electron density on the central metal atom of these complexes plays an important role in deciding the ligand binding sites.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
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Herein, we have formulated the concept of systematic derivatization of a structural motif via C-H bond functionalization. This concept may not only serve as a blueprint for new strategies in diversity synthesis but also provide systematic guidance for the identification of unsolved and important synthetic challenges. To illustrate this point, 2-phenylimidazole was selected as the core motif for this study, a choice inspired by numerous azole-based synthetics, including pharmaceuticals (compound SB 202190), and also fluorescent and chemiluminescent probes. We were able to show that systematic and comprehensive arylation of the 2-phenylimidazole core was feasible, and in the context of this study new arylation methods were developed. The direct 4-arylation of free 2-phenylimidazole was achieved with iodoarenes as the aryl donors in the presence of palladium catalyst (Pd/Ph3P) and magnesium oxide as the base. A complete switch from C-4 to C-2? arylation was accomplished using a ruthenium catalyst [CpRu(Ph3P)2Cl] and CS 2CO3. The corresponding transformations for (N,2)-diphenylimidazole (C-5 and C-2? arylation) were accomplished via the palladium-based method [Pd(OAc)2/Ph3P/CS 2CO3] and a rhodium-catalyzed procedure [Rh(acac)(CO) 2/CS2CO3], respectively. All of the arylation methods described herein demonstrated broad synthetic scope, high efficiency, and exclusive selectivity. Furthermore, these new methods proved to be orthogonal to one another and applicable to sequential arylation schemes. With these methods in hand, arrays of arylated imidazoles may now be accessed in a direct manner from 2-phenylimidazole. This strategy stands in sharp contrast to a traditional approach, wherein a distinct and multistep synthesis would be required for each analogue.

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Reference:
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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We report a new catalytic synthesis of alpha-pyridones and 3(2H)-isoquinolones from readily available 3-en-5-ynyl nitrones and o-alkynylphenyl nitrones; the reaction mechanism is proposed to involve iminyl ketene species through an oxygen transfer process.

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