Ruthenium(II) Tris-Pyrazolylmethane Complexes in Transfer Hydrogenation Reactions

While ruthenium(II) arene complexes have been widely investigated for their potential in catalytic transfer hydrogenation, studies on homologous compounds replacing the arene ligand with the six-electron donor tris(1-pyrazolyl)methane (tpm) are almost absent in the literature. The reactions of [RuCl(κ3-tpm)(PPh3)2]Cl, 1, with a series of nitrogen ligands (L) proceeded with selective PPh3 mono-substitution, affording the novel complexes [RuCl(κ3-tpm)(PPh3)(L)]Cl (L=NCMe, 2; NCPh, 3; imidazole, 4) in almost quantitative yields. Products 2–4 were fully characterized by IR and multinuclear NMR spectroscopy, moreover the molecular structure of 4 was ascertained by single crystal X-ray diffraction. Compounds 2–4 were evaluated as catalytic precursors in the transfer hydrogenation of a series of ketones with isopropanol as the hydrogen source, and 2 exhibited the highest activity. Extensive NMR experiments and DFT calculations allowed to elucidate the mechanism of the transfer hydrogenation process, suggesting the crucial role played by the tpm ligand, reversibly switching from tri- to bidentate coordination during the catalytic cycle

Innovative biorefinery process for the fractionation and conversion of giant reed to carotenoids and triglycerides

Innovative biorefinery process for the fractionation and conversion of giant reed to carotenoids and triglyceride

Soil selenium (Se) biofortification changes the physiological, biochemical and epigenetic responses to water stress in Zea mays L. by inducing a higher drought tolerance

Requiring water and minerals to grow and to develop its organs, Maize (Zea mays L.) production and distribution is highly rainfall-dependent. Current global climatic changes reveal irregular rainfall patterns and this could represent for maize a stressing condition resulting in yield and productivity loss around the world. It is well known that low water availability leads the plant to adopt a number of metabolic alterations to overcome stress or reduce its effects. In this regard, selenium (Se), a trace element, can help reduce water damage caused by the overproduction of reactive oxygen species (ROS). Here we report the effects of exogenous Se supply on physiological and biochemical processes that may influence yield and quality of maize under drought stress conditions. Plants were grown in soil fertilized by adding 150 mg of Se (sodium selenite). We verified the effects of drought stress and Se treatment. Selenium biofortification proved more beneficial for maize plants when supplied at higher Se concentrations. The increase in proline, K concentrations and nitrogen metabolism in aerial parts of plants grown in Se-rich substrates, seems to prove that Se-biofortification increased plant resistance to water shortage conditions. Moreover, the increase of SeMeSeCys and SeCys2 forms in roots and aerial parts of Se-treated plants suggest resistance strategies to Se similar to those existing in Se-hyperaccumulator species. In addition, epigenetic changes in DNA methylation due to water stress and Se treatment were also investigated using methylation sensitive amplified polymorphism (MSAP). Results suggest that Se may be an activator of particular classes of genes that are involved in tolerance to abiotic stresses. In particular, PSY (phytoene synthase) gene, essential for maintaining leaf carotenoid contents, SDH (sorbitol dehydrogenase), whose activity regulates the level of important osmolytes during drought stress and ADH (alcohol dehydrogenase), whose activity plays a central role in biochemical adaptation to environmental stress. In conclusion, Se-biofortification could help maize plants to cope with drought stress conditions, by inducing a higher drought tolerance

Post-Modification of the Electronic Properties by Addition of π-Stacking Additives in N-Heterocyclic Carbene Complexes with Extended Polyaromatic Systems

A series of iridium complexes containing phenanthro[4,5-abc]phenazino[11,12-d]imidazol-2-ylidene and acetonaphtho[1,2-b]quinoxaline[11,12-d]imidazol-2-ylidene ligands have been obtained and fully characterized. These complexes display highly extended polyaromatic systems attached to the backbone of the N-heterocyclic carbene. The presence of this extended polyaromatic system makes the electron-donating character of these ligands sensitive to the presence of π-stacking additives, such as pyrene and hexafluorobenzene. The computational studies predict that the addition of pyrene affords an increase of the electron-donating character of the polyaromatic ligand (TEP decreases), while the addition of hexafluorobenzene has the opposite effect (TEP increases). This prediction is experimentally corroborated by IR spectroscopy, by measuring the shift of the CO stretching bands of a series of IrCl(NHC)(CO)2 complexes, where NHC is the N-heterocyclic carbene ligand with the polyaromatic system. Finally, the energy of the π-stacking interaction of one of the key Ir(I) complexes with pyrene and hexafluorobenzene has been estimated by using the Benesi-Hildebrand treat-ment, based on the δ-shifts observed by 1H NMR spectroscopy.MEC of Spain (CTQ2011-24055/BQU

La Corse alpine : de la subduction-collision à l'extension post-orogénique sur un transect Balagne-Tenda-Cap Corse

La Corse alpine : de la subduction-collision à l'extension post-orogénique sur un transect Balagne-Tenda-Cap Cors

Niobium(V) oxido tris-carbamate as easily available and robust catalytic precursor for the selective sulfide to sulfone oxidation

The oxidation of the sulfide function promoted by a variety of vanadium compounds has been largely explored, whereas the use of homogeneous catalytic systems based on the heavier group 5 metals remains less explored. We report the use of easily available niobium and tantalum carbamates, i.e. [M(O2CNMe2)5] (M = Nb, 1; M = Ta, 2), [Nb(O2CNMe2)4], 3, [NbO(O2CNEt2)3], 4, and [NbCl3(O2CNEt2)2], 5, as effective catalysts for the conversion of a series of alkyl aryl and aromatic sulfides into the corresponding sulfones. NMR investigations on the performant niobium catalyst 4 unexpectedly revealed the substantial stability of this compound in the protic catalytic environment, and a plausible catalytic cycle was obtained by DFT studies. The two active catalytic species, i.e. 4 and its minor mono-methoxide derivative, presumably interconvert to each other exploiting the versatile coordination of the carbamato ligand

Depolymerization of polyethylene terephthalate (PET) under mild conditions by Lewis/Brønsted acidic deep eutectic solvents

Modern society urgently needs new recycling methods to handle the impressive amount of plastic items that are annually discarded. Deep Eutectic Solvents (DESs) have shown interesting results in the depolymerization of polyethylene terephthalate (PET), but most of the procedures still need harsh conditions of temperature and pressure. In this contribution, we propose a bifunctional Lewis/Brønsted acidic DES composed of FeCl3⋅6H2O, cheap and scarcely toxic, in combination with a variety of acids, both mineral and organic, including some of natural origin (citric and acetic acid). We show that the LBDES formed with methanesulfonic acid and paratoluenesulfonic acid are capable of quantitatively depolymerizing PET under mild conditions, with a temperature of 100 ◦C and a reaction time of 1 h, affording high purity terephthalic acid in high yield. For acetic acid, a reaction time of 3 h are necessary to obtain a quantitative depolymerization. Different strategies to optimize the PET/LBDES ratio has been successfully tested, as the consecutive addition of multiple aliquots of PET or the filtration and reuse of the solvent. The best solvent has been characterized through the comparison of theoretical and experimental eutectic phase diagram, confirming its nature of DES

Activation of a bis(phenoxy-amine) precatalyst for olefin polymerisation: First evidence for an outer sphere ion pair with the methylborate counterion

A bis(phenoxy-amine)ZrMe2 complex (1) was synthesized and activated with B(C6F5)3 obtaining an ion pair (2) having the MeB(C6F5)3- counterion in the second coordination sphere as deduced by NMR studies. Both DFT calculations and NMR investigations suggest that the activation is coupled with a change of the binding modality of the tetradentate ligand from cis(N,N)-trans(O,O) in the octahedral dimethyl precursor 1 to cis(N, N)-cis(O,O) in the ion pair 2. © 2009 The Royal Society of Chemistry

Effect of Rhenium(i) Complexation on Aza-Michael Additions to 5-Amino-1,10-Phenanthroline with [ 18 F]Ethenesulfonyl Fluoride towards PET Optical Tracer Development

Conjugations with the recently developed [ 18 F]ethenesulfonyl fluoride ([ 18 F]ESF) were performed on 5-Amino-1,10-phenanthroline, in its free form and coordinated to a rhenium(i) tricarbonyl complex, as a means of radiosynthesizing dual-modal optical and positron emission tomography (PET) tracers. The Michael-donating ability of the aromatic amine was noticeably perturbed on coordination with the rhenium(i) centre, resulting in decreased radiochemical yields from 34 %, in the case of the free ligand, to 1 %. We attribute the decreased nucleophilicity of the amine to metal deactivation from the electron-withdrawing feature of the rhenium(i) tricarbonyl centre, based on spectroscopic and computational evidence, thus highlighting this effect as a crucial parameter in designing late-stage metal coordination methods employing related aza-Michael additions. Photophysical analyses were also performed on the ESF-conjugated rhenium(i) complex, exhibiting a longer decay lifetime from the triplet metal-To-ligand charge transfer excited state when compared with the non-conjugated analogue