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Optically active transition metal complexes. XCVIII. Synthesis and structure of diastereomers of <(-)-Norphos>Ru(II)(eta5-C5H5)I

Two diastereomers of the <(-)-Norphos>Ru(II) complex with eta5-C5H5 and iodide as ligands were synthesized by a phosphine-exchange reaction between (Ph3P)2Ru(II)(eta5-C5H5)Cl and (2R,3R)-(-)-Norphos, followed by Cl/I displacement.Each of the diastereomers can be separated and their structures and chiroptical properties are discussed on the basis of 1H NMR spectroscopy, circular dichroism, and X-ray crystallography.

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

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Reactions of ruthenium Cp phosphine complex with 4,4-disubstituted-1,6- enynes: Effect of methyl substituents in the olefinic fraction

We studied chemical reactions of Cp(PPh3)2RuCl with nine 1,6-enyne compounds (1-4, 8, 12, 19, 21, and 22) in which the triple bond is associated with propargylic alcohol and the olefinic group has various substituted methyl groups. For the enyne compounds 1-3 with no substituted methyl group, the reaction takes place at the propargylic alcohol first giving the allenylidene complex 6 which could undergo a skeletal rearrangement to yield the disubstituted vinylidene complex 7. By changing the propargylic alcohol to propargylic ether, the reaction gives the carbene complex 10 as the major product and the butadiene complex 9 by a cyclization reaction as the minor product. For enyne 12 with two methyl groups at the terminal carbon of the olefinic part, formation of either of the carbene complexes 15 and 16 with a substituted cyclopentenyl ring at Calpha or the vinylidene complex 17 is controlled by the use of solvent. For the formation of 15 and 16, a C-C bond-forming cyclization reaction is proposed to occur at Cbeta in an intermediate where the triple bond is pi-coordinated. However, for the vinylidene intermediate, the reaction may proceed by the formation of the allenylidene, which undergoes a retro-ene reaction to bring about cleavage of the dimethyl substituted allyl group giving 17. For two enynes 21 and 22 where each olefinic portion is internally substituted with one methyl group, two vinylidene complexes 23 and 24 each with a five-membered ring bonded at Cbeta are isolated. The reaction proceeds via formation of an allenylidene intermediate followed by a cyclization at Cgamma. Stabilization of the cationic charge by the presence of methyl subsituents clearly controls the reaction pathway to give different products. These chemical reactions and their mechanisms are corroborated by structure determinations of five ruthenium complexes using single crystal X-ray diffraction analysis.

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

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Caenorhabditis elegans as a model for exploring the efficacy of synthesized organoruthenium complexes for aging and Alzheimer’s disease a neurodegenerative disorder: A systematic approach

The current article deals with the preparation and characterisation of new organoruthenium(II) complexes, namely [RuCp(Dea-Sal-tsc)(PPh3)] (1), [RuCp(Dea-Sal-mtsc)(PPh3)] (2), [RuCp(Dea-Sal-etsc)(PPh3)] (3) and [RuCp(Dea-Sal-ptsc)(PPh3)] (4). The new ruthenium(II) complexes were characterized by various analytical, spectral techniques. The structure of the ligand [H2-Dea-Sal-tsc] and the complex [RuCp(Dea-Sal-tsc)(PPh3)] (1) were confirmed by X-ray crystallography. The complexes (1?4) were used to study the toxicity, stress resistance, aging and neuro-protective effects by taking Caenorhabditis elegans as model. In?vitro free radical scavenging activity was performed by DPPH free radical scavenging assay, the complexes (1?4) exhibited highest scavenging activity than standard Vitamin C (IC50?=?5.28?¡À?0.10). The lifespan has increased over 22.4% in mev-1 mutant worms treated with complex 4. The complex 4 triggered the DAF-16 nuclear localization, increases sod-3 expression and reduced amyloid (Abeta) protein induced paralysis were observed. In the present study we confirmed that oxidative stress resistance of N2 and lifespan extension of mev-1 mutant which showed the potential ROS scavenging activity of complex 4. The results also confirmed the effective anti-aging potential of ruthenium complex 4 which may be developed as a therapeutic drug for the prevention of aging and age related neurodegenerative diseases. Further studies are required to find out the exact action of complex 4 on higher model.

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

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Reactions of (L = PPh3, AsPh3, or SbPh3; L2 = Ph2PCH2CH2PPh2 or Ph2PCH2PPh2) with 1,4-Piperazinedicarbonitrile or 1-Piperidinecarbonitrile in the Presence of an Anion (BF4(1-), PF6(1-), BPh4(1-), or ClO4(1-))

Reactions of (L = PPh3, AsPh3, or SbPh3; L2 = Ph2PCH2CH2PPh2 or Ph2PCH2PPh2) have been carried out with 1-piperidinecarbonitrile or 1,4-piperazinedicarbonitrile in the presence of a suitable anion (PF6(1-), BF4(1-), BPh4(1-), or ClO4(1-)).The products were found to be cationic mono- and bi-nuclear complexes which have been characterised by elemental analyses and spectroscopic (i.r., u.v.-visible, and n.m.r.) studies.Conductivity measurements have also been carried out to confirm the charges on these cationic species.

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

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Dimeric ruthenium complexes with C5H2 and C5H bridges

Treatment of [Cp*Ru(dppe)]BF4 with 0.5 equiv of HC?CCH(OH)C?CH in THF led to the formation of the C5H2-bridged compound [Cp*(dppe)-Ru=C=C=CHCH=C=Ru(dppe)Cp*](BF4)2. The C5H2-bridged compound reacted with alumina to give the C5H2-bridged compound [Cp*(dppe)Ru=C=C=CHC?CRu-(dppe)Cp.*]BF4. These reactions were extended to prepare the analogous complex [Cp(PPh3)2Ru=C=C= CHC?CRu(PPh3)2Cp]BF4.

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

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Syntheses of transition metal methoxysiloxides

The paper describes three methods for the preparation of methoxysiloxide complexes, a rare class of complexes of relevance to room temperature vulcanization (RTV) of polysiloxanes. The salt metathesis reaction involves the use of the recently described reagent NaOSi(OMe)2Me with various metal chlorides to give Cp?2Ti[OSi(OMe)2Me](OMe), (Me,MeN2N)NiOSi(OMe)2Me, (IPr)CuOSi(OMe)2Me, and (triphos)CoOSi(OMe)2Me (Cp? = C5Me5, triphos = Me(CH2PPh2)3). Several attempted reactions gave methoxide complexes instead, a pathway that is attributed to the intermediacy of kappa2-OSi(OMe)2Me species. The diol Cp?2Zr(OH)2 reacts with excess (MeO)3SiMe to give Cp?2Zr[OSi(OMe)2Me]2. In contrast the less nucleophilic Cp?2Ti(OH)2 was unreactive. The third route to methoxysiloxide complexes involves the reaction of Cp?2M(O)(py) with (MeO)3SiMe to give Cp?2M[OSi(OMe)2Me](OMe) in nearly quantitative yield (M = Ti, Zr). The structures of Cp?2Ti[OSi(OMe)2Me](OMe), Cp?2Zr[OSi(OMe)2Me](OMe), (IPr)CuOSi(OMe)2Me, and (triphos)CoOSi(OMe)2Me were confirmed by single crystal X-ray diffraction.

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

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Dimerisation and reactivity of HCCCCFc at ruthenium centres

In contrast to the simple diynyl complexes formed in reactions between HCCCCFc and MCl(dppe)Cp; (M = Fe, Ru), an analogous reaction with RuCl(PPh 3)2Cp; in the presence of KPF6 and dbu resulted in dimerisation of the diyne at the Ru centre to afford a mixture of [Ru{eta1,eta2-C(CCFc)C(L)CHCCCHFc}(PPh 3)Cp]PF6 (L = dbu 1, PPh3 2). Similar reactions with RuCl(PR3)2L gave [Ru{eta1, eta2-C(CCFc)C(dbu)CHCCCHFc}(PR3)L]PF6 (L = Cp, R = Ph 3, m-tol 4; L = eta5-C9H7, R = Ph 5). The reaction between 3 and I2, followed by crystallization of the paramagnetic product from MeOH, afforded the dicationic [Ru{C(CCFc)C(dbu) CHC(OMe)C(OMe)CHFc}(PPh3)Cp](I3)2 6. The molecular structures of 2¡¤2CH2Cl2 and 6.S (S = 2CH2Cl2, C6H6) were determined by single-crystal XRD studies.

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

A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru. In a Article£¬once mentioned of 32993-05-8, Safety of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

Preparation of ruthenium silanethiolato complexes and their reactions with sulfur dioxide; possible models for the activation of SO2 in the homogeneously catalyzed Claus reaction

CpRu(PPh3)2SSiiPr3 (6a) was prepared by reacting [CpRu(PPh3)2(acetone)]BF4 and NaSSiiPr3. Complex 6a is substitution-labile and readily gave the mixed-ligand derivatives CpRu(PPh3)(L)SSiiPr3, where L = CO (6b), PMe3 (6c), P(OMe)3 (6d), upon treatment with the corresponding ligands. CpRu(dppe)SSiiPr3 (6e) was obtained from complex 6a and dppe via the intermediate formation of CpRu(PPh3)(eta1-dppe)SSiiPr3. Treatment of complex 6a with one equivalent of SO2 gave primarily unstable CpRu(PPh3)(SO2)SSiiPr3 (6f). However, complexes 6b-e inserted one equivalent of SO2 solely at their S-SiiPr3 function to give the unstable O-silyl thiosulfito complexes CpRu(PPh3)(L)SS(O)OSiiPr3 (L = CO (8b), PMe3 (8c), P(OMe)3 (8d)) as well as CpRu(dppe)SS(O)OSiiPr3 (8e). The S-H bonds of CpRu(PPh3)2SH (7a) and CpRu(dppe)SH (7b) added to PhNSO to give CpRu(PPh3)2SS(O)NHPh (9a) and CpRu(dppe)SS(O)NHPh (9b), respectively. The crystal structure of complex 6a was determined. Crystallographic data for 6a: triclinic, P1, a = 10.642(6) A?, b = 11.068(8) A?, c = 21.994(10) A?, alpha = 79.27(5), beta= 89.22(5), gamma = 62.32(4), V = 2246(2) A?3, Z = 2.

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

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Mono(eta5-cyclopentadienyl)metal(II) complexes with thienyl acetylide chromophores: Synthesis, electrochemical studies, and first hyperpolarizabilities

A series of mono(eta5-cyclopentadienyl)metal-(II) complexes with nitro-substituted thienyl acetylide ligands of general formula [M(eta5 -C5H5)(L)(C?C{C4H2S}nNO2)] (M = Fe, L = K2 -DPPE, n = 1, 2; M = Ru, L= K2 -DPPE, 2 PPh3, n = 1, 2; M = Ni, L = PPh3, n = 1, 2) has been synthesized and fully characterized by NMR, FT-IR, and UV – Vis spectroscopy. The electrochemical behavior of the complexes was explored by cyclic voltammetry. Quadratic hyperpolarizabilities (beta) of the complexes have been determined by hyper-Rayleigh scattering (HRS) measurements at 1500 nm. The effect of donor abilities of different organometallic fragments on the quadratic hyperpolarizabilities was studied and correlated with spectroscopic and electrochemical data. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations were employed to get a better understanding of the second-order nonlinear optical properties in these complexes. In this series, the complexity of the push-pull systems is revealed; even so, several trends in the second-order hyperpolarizability can still be recognized. In particular, the overall data seem to indicate that the existence of other electronic transitions in addition to the main MLCT clearly controls the effectiveness of the organometallic donor ability on the second-order NLO properties of these push-pull systems. (Figure Presented)

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

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Combined effects of metal and ligand capable of accepting a proton or hydrogen bond catalyze anti-Markovnikov hydration of terminal alkynes

A binding pocket for water is created in 1 by the imidazolyl phosphane ligands and the Ru11 center. Compound 1 proves to be an excellent catalyst for a highly selective anti-Markovnikov hydration of terminal alkynes to give aldehydes rather than isomeric ketones under near-neutral conditions (aldehyde-to-ketone ratio up to 1000:1).

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