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Photoinduced electron transfer kinetics of linked Ru-Co photocatalyst dyads

Two new supramolecular photocatalyst dyads based on the [Ru(2,2?-bipyridine)3]2+ photosensitizer linked to a macrocyclic Co(II)tetra(pyridyl) catalyst for proton reduction are reported. The dyads differ primarily in the bridging ligand which links the molecular modules; the first being a short and flexible linker, and the second a longer and electronically conjugated linker. Ultrafast transient optical spectroscopy was used to monitor the photoinduced kinetics of the dyads following visible excitation of the photosensitizer module. Direct comparison of transient spectra and kinetics indicates that there are indeed substantial differences between the ultrafast transient optical spectroscopy of the dyads, but there is no indication of oxidative quenching of the photosensitizer module by the catalyst module. These initial design and characterization studies of the linked Ru(II)?Co(II) dyads provide an important foundation for advanced designs of systems for efficient solar energy conversion by molecular architectures.

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

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Syntheses and quadratic hyperpolarizabilities of some (pyridylalkynyl)metal complexes: Crystal structures of [Ni{2-(C?C)C5H3NNO2-5}(PPh 3)(eta-C5H5)], [Au{2-(C?C)C5H3NNO2-5}(PPh3)] and [Au{2-(C?C)C5H4N}(PPh3)]

The complexes [Ru{2-(C?C)C5H3NR-5}(PPh3) 2(eta-C5H5)] (R = NO2 1 or H 2), [Ni{2-(C?C)C5H3NR-5}(PPh3)-(eta-C 5H5)] (R = NO23 or H 4) and [Au{2-(C?C)C5H3NR-5}L] (L = PPh3, R = NO2 5 or H 6; L = PMe3, R = NO2 7) have been synthesized and 3, 5 and 6 structurally characterized; no significant increase in quinoidal vinylidene contribution to the acetylide ground-state structure is apparent on progression from structurally characterized phenylacetylide complexes to the new pyridylacetylide complexes, or upon replacement of 5-H by 5-NO2 in progressing from 6 to 5. The molecular quadratic optical non-linearities of 1-7 have been determined by hyper-Rayleigh scattering (HRS). The HRS measurements at 1064 nm are consistent with an increase in beta upon replacement of phenyl by an N-heterocyclic ring (replacing a nitrophenylacetylide by a nitropyridylacetylide ligand) for the ruthenium and gold systems, but with no change for the nickel complexes, and with an increase in non-linearity upon replacement of PMe3 by PPh3 in progressing from 7 to 5. The bulk second-order susceptibilities of the series have been determined by Kurtz powder measurements at 1054 nm, with the only significant response (about eight times that of urea) being that of 3; this complex was the only one of the three structurally characterized to pack non-centrosymmetrically in the crystal lattice. Electrochemical data for 1-4 have been obtained; comparison to analogous nitrophenylacetlylide complexes reveals that replacing nitrophenylacetylide by nitropyridylacetylide leads to a significant increase in MII/III oxidation potential for the ruthenium complexes, but to no change for the nickel examples. The parameter EoMII/II -EoNO2/NO2 – was evaluated for 1-4, results for M = Ru vs. Ni being consistent with experimentally determined non-linearities, i.e. smaller DeltaEo and larger non-linearities for ruthenium vs. nickel.

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

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FUNCTIONALIZED LINEAR AND CYCLIC POLYOLEFINS

This invention relates to methods and compositions for preparing linear and cyclic polyolefins. More particularly, the invention relates to methods and compositions for preparing functionalized linear and cyclic polyolefins via olefin metathesis reactions. Polymer products produced via the olefin metathesis reactions of the invention may be utilized for a wide range of materials applications. The invention has utility in the fields of polymer and materials chemistry and manufacture.

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

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Relative stability of half-sandwich eta6-benzene Ru(II) complexes of tridentate (2-pyridyl)alkylamine ligands of varying chelate ring-size: Nucleophilic addition of hydride ion onto the benzene ring

A full account of half-sandwich complexes of ruthenium(II) having three-legged “piano-stool” geometry supported by tridentate (2-pyridyl)alkylamine ligands is presented. Reaction of the dimer [{(eta6-C6H6)RuCl(mu-Cl)}2] with N-methyl-N,N-bis(2-pyridylmethyl)amine (MeL*) in CH3OH in the presence of NH4PF6 affords the complex [(eta6-C6H6)Ru(MeL*)][PF6]2 (1). A similar reaction with N-methyl-N,N-bis(2-pyridylethyl)amine (MeL**), however, affords a non-organometallic Ru(III)-dimeric complex [(MeL* *)2 Ru2III (mu -O) (mu -Cl) Cl2] [PF6] (5) (the composition of this complex has been established by physicochemical method). Nucleophilic addition reaction on 1 with NaBH4 leads to the isolation of a cyclohexadienyl complex [(eta5-C6H7)Ru(MeL*)][PF6] (3). The molecular structure of 1 ¡¤ 2CH3CN, 3, and previously reported cyclohexadienyl complex [(eta5-C6H7)Ru(MeL)][PF6] (4) [MeL = N-methyl-[(2-pyridyl)ethyl(2-pyridyl)-methyl]amine], obtained from the reaction between NaBH4 and previously reported “piano-stool” complex [(eta6-C6H6)Ru(MeL)][PF6]2 (2), has been confirmed by X-ray crystallography. Solution-state structure of new complexes 1 and 3 has been elucidated by their 1H NMR spectra in CD3CN. The behavior of complex 3 has been investigated with the aid of two-dimensional 1H NMR spectroscopy, as well. An attempt has been made to provide a rationale for the effect of supporting tridentate N-donor ligand [MeL, MeL*, and MeL**], varying in the chelate ring-size on (i) the relative stability of half-sandwich eta6-benzene Ru(II) complexes and (ii) the electrophilicity of Ru(II)-coordinated benzene ring on the nucleophilic addition 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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Synthesis of the first chiral PNA monomer labelled with a Fischer-type carbene complex

The synthesis, through a cross-metathesis reaction, of the first chiral peptide nucleic acid (PNA) monomer labelled with a Fischer-type carbene complex of chromium is reported. IR analysis of the new bioconjugate shows that the Cr(CO)4 moiety represents a suitable spectroscopic probe for diagnostic purposes.

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

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Synthesis of ruthenium vinylidene complexes with dppe ligand and their cyclopropenation reaction

A number of cationic ruthenium vinylidene complexes [Ru]=C=C(Ph)CH2R+ ([Ru]=(eta5-C5H5)(dppe)Ru, dppe=Ph2PCH2CH2PPh2, 5a, R=CN; 5b, R=C6F5; 5c, R=Ph; 5d, R=p-C6H4CN; 5e, R=p-C6H4CF3; 5f, R=1-C10H7; 5g, R=CO2CH3) are prepared from electrophilic addition of organic halides to the acetylide complex [Ru]-CCPh at the boiling point of CHCl3. Complex 5g?, prepared at room temperature, displays similar spectroscopic property as that of 5g but is easily hydrolyzed to give [Ru]COCH2Ph (6). Cyclopropenation of the organic vinylidene moiety of 5a-5f is accomplished in acetone by deprotonation of 5 with n-Bu4NOH yielding the neutral cyclopropenyl complexes (7a, R=CN; 7b, R=C6F5; 7c, R=Ph; 7d, R=p-C6H4CN; 7e, R=p-C6H4CF3; 7f, R=1-10H7). Protonation of 7b-7f regenerates the corresponding vinylidene complexes. In the presence of allyl iodide, opening of the three-membered ring of 7a, followed by a subsequent oxidative coupling reaction, gives a dimeric dicationic product {[Ru]=C=C(Ph)-CHCN}2+2 (9a). In the processes of preparing the starting material Cp(dppe)RuCl for the acethylide complex, two dppe complexes Ru(dppe)2Cl2 (2) and [Cp(dppe)RuCl]2 (3) are isolated. Molecular structures of complexes 2, 3, 6, and 7b have been confirmed by X-ray diffraction analysis.

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

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15746-57-3, Name is Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II), molecular formula is C20H16Cl2N4Ru, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 15746-57-3, HPLC of Formula: C20H16Cl2N4Ru

Long Range Photoinduced Electron Transfer in a Rigid Polymer

Electron (hole) tunnelling reactions are studied in a rigid polymer medium by following the reductive quenching of a series of Ru(LL)3(2+)* homologues by a series of aromatic amines.Tunnelling distances up to 12 Angstroem (edge to edge) are observed.The experimental data include a determination of the exponential damping factor alpha in the electronic term (Hab).The data are consistent with a weak dependence of alpha on binding energy.Such a weak dependence is more consistent with a superexchange description than with a barrier tunnelling description of electron (hole) transfer.These reactions are shown to be essentially temperature independent between 298 K and 359 K, but are significantly slower at 77 K.

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

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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. 246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu. In a Article£¬once mentioned of 246047-72-3, Recommanded Product: 246047-72-3

Stereoselective synthesis of the C1-C8 subunit of peloruside A

Two routes to the C1-C8 subunit of peloruside A are disclosed. The first route involving 14 steps exploits Krische’s allylation, substrate controlled 1,3-asymmetric induction during bromohydrin formation from an alkene utilizing an intramolecular sulfinyl group as a nucleophile and Pummerer reaction as key steps. The second, shorter, scalable route (seven steps) exploits catalytic asymmetric reactions including Jacobsen’s hydrolytic kinetic resolution of an epoxide and Sharpless’ asymmetric dihydroxylation reaction as the key steps.

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

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Enyne metathesis for the formation of macrocyclic 1,3-dienes

Macrocyclic 1,3-dienes of a variety of ring sizes are formed in good yield via enyne metathesis. Both endo- and exo-products are observed depending on the size of the macrocycle. In general, 10-membered rings and smaller give exo-products, while 12-membered rings and larger give endo-products. The endo/exo selectivity and the E/Z ratio of the diene products can be further controlled by the presence of ethylene in the reaction. Copyright

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

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Mechanistic investigations on the hydrogenation of alkenes using ruthenium(II)-arene diphosphine complexes

The ruthenium(II) complexes [Ru(eta2-P-P)(eta6-p- cymene)Cl]Cl, P-P = diphenylphosphinomethane (dppm), diphenylphosphinoethane (dppe), or diphenylphosphinopropane (dppp), and the highly water-soluble analogues, [Ru(eta2-P-P)(eta6-arene)Cl]Na3, P-P = 1,2-bis(di-4-sulfonatophenylphosphino)benzene (dppbts), arene = p-cymene, benzene, or [2.2]paracyclophane, are efficient catalyst precursors for the hydrogenation of styrene in an aqueous biphase. By the use of high gas pressure NMR techniques and electrospay ionization mass spectrometry, the active species in the hydrogenation have been indirectly identified to be a dihydrogen complex, which also catalyzes H/D isotope exchange. Using the ruthenium(II) dppbts derivatives as precatalysts, evidence is provided for an arene exchange process that takes place during the catalytic hydrogenation of styrene. Together, these results lead to the proposition of a catalytic cycle for the hydrogenation of the C=C double bond of styrene using ruthenium(II)-arene diphosphine complexes.

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