Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

New aryloxybenzylidene ruthenium chelates - synthesis, reactivity and catalytic performance in ROMP.

ABSTRACT: New phenoxybenzylidene ruthenium chelates were synthesised from the second generation Grubbs catalysts bearing a triphenylphosphine ligand (or its para-substituted analogues) by metathesis exchange with substituted 2-vinylphenols. The complexes behave like a latent catalyst and are characterized by an improved catalytic behaviour as compared to that of the known analogues, i.e., they exhibit high catalytic inactivity in their dormant forms and a profound increase in activity after activation with HCl. The strong electronic influence of substituents in the chelating ligand on the catalytic activity was demonstrated. The catalytic properties were tested in ROMP of cyclooctadien (COD) and a single selected norbornene derivative.

SUBMITTER: Zak P

PROVIDER: S-EPMC4660962 | biostudies-literature | 2015

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

New aryloxybenzylidene ruthenium chelates - synthesis, reactivity and catalytic performance in ROMP.

Żak Patrycja P Rogalski Szymon S Majchrzak Mariusz M Kubicki Maciej M Pietraszuk Cezary C

Beilstein journal of organic chemistry 20151014

New phenoxybenzylidene ruthenium chelates were synthesised from the second generation Grubbs catalysts bearing a triphenylphosphine ligand (or its para-substituted analogues) by metathesis exchange with substituted 2-vinylphenols. The complexes behave like a latent catalyst and are characterized by an improved catalytic behaviour as compared to that of the known analogues, i.e., they exhibit high catalytic inactivity in their dormant forms and a profound increase in activity after activation wit ...[more]

PMID: 26664610

Similar Datasets

Ruthenium (II) and Iridium (III) Complexes of N-Heterocyclic Carbene and Pyridinol Derived Bidentate Chelates: Synthesis, Characterization, and Reactivity.

Project description:We report the synthesis and characterization of new ruthenium(II) and iridium(III) complexes of a new bidentate chelate, NHCR'-pyOR (OR = OMe, OtBu, OH and R' = Me, Et). Synthesis and characterization studies were done on the following compounds: four ligand precursors (1-4); two silver complexes of these NHCR'-pyOR ligands (5-7); six ruthenium complexes of the type [η6-(p-cymene)Ru(NHCR'-pyOR)Cl]X with R' = Me, Et and R = Me, tBu, H and X = OTf-, PF6- and PO2F2- (8-13); and two iridium complexes, [Cp*Ir(NHCMe-pyOtBu)Cl]PF6 (14) and [Cp*Ir(NHCMe-pyOH)Cl]PO2F2 (15). The complexes are air stable and were isolated in moderate yield. However, for the PF6- salts, hydrolysis of the PF6- counter anion to PO2F2- during t-butyl ether deprotection was observed. Most of the complexes were characterized by 1H and 13C-NMR, MS, IR, and X-ray diffraction. The ruthenium complexes [η6-(p-cymene)Ru(NHCMe-pyOR)Cl]OTf (R = Me (8) and tBu (9)) were tested for their ability to accelerate CO2 hydrogenation and formic acid dehydrogenation. However, our studies show that the complexes transform during the reaction and these complexes are best thought of as pre-catalysts.

| S-EPMC5714516 | biostudies-literature

ROMP from ROMP: A New Approach to Graft Copolymer Synthesis.

Project description:A new strategy is presented for the synthesis of graft copolymers using only the ring-opening metathesis polymerization (ROMP). From a ROMP-derived main chain, pendant maleimide functional groups are converted into norbornene moieties via a Diels-Alder reaction with cyclopentadiene. The norbornene groups serve as sites of initiation, and subsequent ROMP from the main chain yields graft copolymers with both main and side chains derived from ROMP. This strategy offers ready access to defined graft copolymers.

| S-EPMC2784692 | biostudies-literature

Ruthenium-based PACT agents based on bisquinoline chelates: synthesis, photochemistry, and cytotoxicity.

Project description:The known ruthenium complex [Ru(tpy)(bpy)(Hmte)](PF6)2 ([1](PF6)2, where tpy = 2,2':6',2″-terpyridine, bpy = 2,2'-bipyridine, Hmte = 2-(methylthio)ethanol) is photosubstitutionally active but non-toxic to cancer cells even upon light irradiation. In this work, the two analogs complexes [Ru(tpy)(NN)(Hmte)](PF6)2, where NN = 3,3'-biisoquinoline (i-biq, [2](PF6)2) and di(isoquinolin-3-yl)amine (i-Hdiqa, [3](PF6)2), were synthesized and their photochemistry and phototoxicity evaluated to assess their suitability as photoactivated chemotherapy (PACT) agents. The increase of the aromatic surface of [2](PF6)2 and [3](PF6)2, compared to [1](PF6)2, leads to higher lipophilicity and higher cellular uptake for the former complexes. Such improved uptake is directly correlated to the cytotoxicity of these compounds in the dark: while [2](PF6)2 and [3](PF6)2 showed low EC50 values in human cancer cells, [1](PF6)2 is not cytotoxic due to poor cellular uptake. While stable in the dark, all complexes substituted the protecting thioether ligand upon light irradiation (520 nm), with the highest photosubstitution quantum yield found for [3](PF6)2 (Φ[3] = 0.070). Compounds [2](PF6)2 and [3](PF6)2 were found both more cytotoxic after light activation than in the dark, with a photo index of 4. Considering the very low singlet oxygen quantum yields of these compounds, and the lack of cytotoxicity of the photoreleased Hmte thioether ligand, it can be concluded that the toxicity observed after light activation is due to the photoreleased aqua complexes [Ru(tpy)(NN)(OH2)]2+, and thus that [2](PF6)2 and [3](PF6)2 are promising PACT candidates.

| S-EPMC8437835 | biostudies-literature

Synthesis, Reactivity, and Catalytic Transfer Hydrogenation Activity of Ruthenium Complexes Bearing NNN Tridentate Ligands: Influence of the Secondary Coordination Sphere.

Project description:By the introduction of -OH group(s) into different position(s) of 6-(pyridin-2-ylmethyl)-2,2'-bipyridine, several NNN-type ligands were synthesized and then introduced to ruthenium (Ru) centers by reactions with RuCl2(PPh3)3. In the presence of PPh3 or CO, these ruthenium complexes reacted with NH4PF6 in CH2Cl2 or CH3OH to give a series of ionic products 5-9. The reaction of Ru(L2)(PPh3)Cl2 (2) with CO generated a neutral complex [Ru(L2)(CO)Cl2] (10). In the presence of CH3ONa, 10 was further converted into complex [Ru(L2)(HOCH3)(CO)Cl] (11), in which there was a methanol molecule coordinating with ruthenium, as suggested by density functional theory calculations. The catalytic transfer hydrogenation activity of all of these new bifunctional metal-ligand complexes was tested. Dichloride complex 2 exhibits best activity, whereas carbonyl complexes 10 and 11 are efficient for selectively reducing 5-hexen-2-one, suggesting different hydrogenation mechanisms. The results reveal the dramatic influence for the reactivity and catalytic activity of the secondary coordination sphere in transition metal complexes.

| S-EPMC6641270 | biostudies-literature

Catalytic resonance of ammonia synthesis by simulated dynamic ruthenium crystal strain.

Project description:Ammonia affords dense storage for renewable energy as a fungible liquid fuel, provided it can be efficiently synthesized from hydrogen and nitrogen. In this work, the catalysis of ammonia synthesis was computationally explored beyond the Sabatier limit by dynamically straining a ruthenium crystal (±4%) at the resonant frequencies (102 to 105+ Hz) of N2 surface dissociation and hydrogenation. Density functional theory calculations at different strain conditions indicated that the energies of NHx surface intermediates and transition states scale linearly, allowing the description of ammonia synthesis at a continuum of strain conditions. A microkinetic model including multiple sites and surface diffusion between step and Ru(0001) terrace sites of varying ratios for nanoparticles of differing size revealed that dynamic strain yields catalytic ammonia synthesis conversion and turnover frequency comparable to industrial reactors (400°C, 200 atm) but at lower temperature (320°C) and an order of magnitude lower pressure (20 atm).

| S-EPMC8791612 | biostudies-literature

Effect of nitrogen co-doping with ruthenium on the catalytic performance of Ba/Ru-N-MC catalysts for ammonia synthesis.

Project description:Nitrogen co-doping with ruthenium mesoporous carbons (Ru-N-MC) was prepared by co-impregnation of sucrose and urea on a RuCl3/SiO2 template followed by a thermal carbonization process. The turnover frequency (TOF) of the Ba/Ru-N-MC catalyst in ammonia synthesis is 0.16 s-1 under reaction conditions of 400 °C, pressure of 10 MPa and space velocity of 10 000 h-1. The superior catalytic performance of the Ba/Ru-N-MC is proposed to originate from the strong metal-support interaction between Ru nanoparticles (NPs) and carbon support. In addition to the activity, the Ba/Ru-N-MC catalyst exhibits a long-term stability for 35 h without significant deactivation.

| S-EPMC9066922 | biostudies-literature

Synthesis, Characterization, and Catalytic Performance of a New Heterobimetallic Y/Tb Metal-Organic Framework with High Catalytic Activity.

Project description:A three-dimensional heterobimetallic porous structure with the formula {[Y3.5Tb1.5L6(OH)3(H2O)1.5 (DMF)1.5] n ·1.5H2O·DMF} n (L = 3-amino-4-hydroxybenzoate) (Y/Tb-MOF) has been synthesized and characterized by single crystal and powder X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX), inductively coupled plasma mass spectrometry (ICP-MS), electrophoretic mobility, and Fourier transform infrared (FTIR) spectroscopy. The structure presents two metal environments: a bioaugmented isosceles wedge (mm2) MO8 and a tricapped trigonal prism (-6m2) MN3O6. These configurations facilitate the creation of channels with a diameter of 10.7 Å, enabling its utilization as an active catalyst where the heterobimetallic nature of the assembly will be explored. This mixed-metal metal-organic framework has been tested in the cycloaddition of epoxides with carbon dioxide as well as in the cyanosilylation and hydroboration reactions of carbonylic substrates. Additionally, a monometallic Tb-MOF analogue has been synthesized for comparative evaluation of their catalytic performances. Both the mixed metal and monometallic variants exhibit outstanding activity in the cyanosilylation and hydroboration of carbonyls and in the synthesis of carbonates under CO2 pressure. However, only the latter exhibits high recyclability.

| S-EPMC11191568 | biostudies-literature

Spherical Silica Modified with Magnesium and Ruthenium-Synthesis, Characterization and Catalytic Properties.

Project description:The design of different bimetallic catalysts is an important area of catalytic research in the context of their possible applications in the cascade processes, meeting the requirements of the so-called green chemistry. In this study, such catalysts were obtained by the incorporation of magnesium species into spherical silica, which was in the next step covered with porous silica and modified with ruthenium species. The structure and chemical composition of the materials obtained were determined by XRD measurements, low temperature N2 adsorption/desorption, SEM, ICP-OES and XPS methods. The catalytic activities of materials obtained were tested in 2-propanol decomposition and hydrogenation of levulinic acid. The results obtained confirmed the successful coverage of nanospheres with porous silica. A much higher concentration of ruthenium species was found on the surface of the catalysts than in their bulk. The opposite relationship was observed for magnesium species. The modification of nanospheres with silica had a positive effect on the catalytic activity of the materials obtained. For the most active sample, i.e., Ru/NS/3Mg/NS, 49% of levulinic acid conversion in its hydrogenation process was reported with γ-valerolactone as the only product.

| S-EPMC8658599 | biostudies-literature

Synthesis and Catalytic Reactivity of Cobalt Pincer Nitrosyl Hydride Complexes.

Project description:The synthesis, characterization, and catalytic activity of low-spin {CoNO}8 pincer complexes of the type [Co(PCP)(NO)(H)] are described. These compounds are obtained either by reacting [Co(PCP)(κ2-BH4)] with NO and Et3N or, alternatively, by reacting [Co(PCP)(NO)]+ with boranes, such as NH3·BH3 in solution. The five-coordinate, diamagnetic Co(III) complex [Co(PCPNMe-iPr)(NO)(H)] was found to be the active species in the hydroboration of alkenes with anti-Markovnikov selectivity. A range of aromatic and aliphatic alkenes were efficiently converted with pinacolborane (HBpin) under mild conditions in good to excellent yield. Mechanistic insight into the catalytic reaction is provided by means of isotope labeling, NMR spectroscopy, and APCI/ESI-MS as well as DFT calculations.

| S-EPMC7842137 | biostudies-literature

Catalytic living ROMP: block copolymers from macro-chain transfer agents.

Project description:Vinyl ether based macro-chain transfer agents (m-CTAs) are used to produce different di or tri-block copolymers under catalytic living ROMP conditions. Polystyrene (PS) vinyl ether m-CTA and polycaprolactone (PCL) or polylactide vinyl ether (PLA) m-CTAs are synthesized straightforwardly via ATRP and ROP respectively. Regioselectivity as well as the high metathesis activity of these m-CTAs enabled us to synthesise a range of metathesis-based A-B diblock copolymers with controlled dispersities (Đ < 1.4). In this manner, PS-ROMP (here, ROMP refers to a poly(MNI-co-DHF) block), PCL-ROMP and PLA-ROMP were synthesized using substoichiometric amounts of ruthenium complex in a living fashion. Also, a more complex PEG-PCL-ROMP tri-block terpolymer was obtained catalytically. All block copolymers were characterized by SEC and DOSY NMR spectroscopy. We believe that this methodology of using macro-chain transfer agents to prepare degradable ROMP polymers under catalytic living ROMP conditions will find applications in biomedicine.

| S-EPMC10262279 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data