Synthesis, Isolation and Characterization of a Triiodo Organometallic Palladium(IV) Complex. Quantitative and Regioselective Synthesis of Two C–I Reductive Elimination Products

©2011. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ This document is the Accepted version of a Published Work that appeared in final form in Inorganic Chemistry. To access the final edited and published work see https://doi.org/10.1021/ic2006869Iodine and the pincer complex [Pd(O,N,C-L)I], where L is the monoanionic ligand resulting from deprotonation of the acetyl group of the dimethylmonoketal of 2,6-diacetylpyridine, are in equilibrium at low temperatures with the Pd(IV) complex [Pd(O,N,C-L)I3], which can be isolated at –40 ºC and characterized by 1H NMR spectroscopy and Xray diffraction studies, in spite of its great instability. When the same reaction is carried out at room temperature, a quantitative reductive elimination process occurs giving L–I, which in the presence of water affords L'–I, resulting from hydrolysis of L–I

Sensitivity of quinoa cv. ‘Titicaca’ to low salinity conditions

Quinoa (Chenopodium quinoa Will.) is an annual herbaceous Andean plant. In recent years there is a growing interest on it due to its high quality as food, its wide adaptation to agroecological conditions and resistance to different abiotic stresses. In this work, we evaluate the growth pattern of quinoa plants cv. ‘Titicaca’, subjected to different levels of salinity, focusing on leaf production and nutrient content. In this sense, the results have shown that a high concentration of salinity negatively affects the growth of quinoa plants. In fact, plants grown with 200 mM NaCl reduced the photosynthetic rate and levels of chlorophylls and carotenoids in comparison with the rest of the treatments. Likewise, it has been proven how the progressive increase in salinity has negative effects on transpiration, stomatal conductance and photosynthetic rate, with significant subsequent reductions in shoot biomass, leaf area and nutrient adquisition, but without a decline in leaf dry weight (DW) production. However, the treatment of 200 mM NaCl demonstrated the best results regarding the water-use efficiency, as well as the number of saline glands. According to our results, the quinoa plant cv. ‘Titicaca’ seems to be tolerant to moderate concentrations of salinity (50–100 mM NaCl). This study could serve as a reference on this little known and cultivated species in the Mediterranean region, since it could become an alternative crop in areas with moderate salinity problems.Luna Morcillo was supported by the Spanish MICINN (PTA2019-018094). CEAM Foundation was funded by the Generalitat Valenciana

Synthesis of Bis-(2,6-dinitroaryl)palladium(II) and Mono-(2,6- dinitroaryl)platinum(II) Complexes. A New Example of the Transphobia Effect and of Transmetallation from Pt to Hg

©2008. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ This document is the Accepted version of a Published Work that appeared in final form in American Chemical Society. To access the final edited and published work see https://doi.org/10.1021/om701077yThe reaction of [Pd(k2-Ar)(O,O-acac)] (k2-Ar = k2-C,O-C6(NO2)2-2,6-(OMe); 1) with one equiv of RNC gives [Pd(k2-Ar)(O,O-acac)(CNR)] [R = Xy (2a), tBu (2b)] and with four equiv of XyNC, trans-[Pd(k1-Ar)2(CNXy)2] (k1-Ar = k1-C,O-C6(NO2)2-2,6-(OMe); 3). These complexes has also been obtained (1) by reacting Tl(acac) with one equiv of trans-[Pd(k1Ar)Cl(CNXy)2] (4), obtained in turn by reacting trans-(NMe4)2[Pd(k1-Ar)Cl(µ-Cl)]2 (5) with four equiv of XyNC or (2) by reacting [Pd(k1-Ar)(C-acac)(phen)] (6) with four equiv of XyNC. cis-[Pt(k2-Ar)(k1-Ar)(PPh3)] (7) reacts (1) with Hg(OAc)2 (1:1) to afford a mixture of [Hg(Ar)(OAc)], cis-[{Pt(k1-Ar)(PPh3)}2(µ-OH)(µ-OAc)] (8) and trans-[{Pt(k1-Ar)(PPh3)}2(µOH)2] (9) or (2) with HgCl2 (1:1) to give trans-[{Pt(k1-Ar)(PPh3)}2(µ-Cl)2] (10), which reacts with excess of Ag(OAc) to give 8. The reaction of 10 with excess of KOH, or with Tl(acac) (1:1) gives 9. Reaction of palladium complex 5 with two equiv of Hg(OAc)2 affords trans[Pd(k2-Ar)(µ-OAc)]2 (11). The crystal structures of 2a, 2b, 3, 5, 8, 9, and 11 have been determined

Homoleptic tris-cyclometalated platinum(iv) complexes: a new class of long-lived, highly efficient 3LC emitters

©. This manuscript version is made available under the CC-BY-NC 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ This document is the, Accepted, version of a Published Work that appeared in final form in Chemical Science. To access the final edited and published work see: https://doi.org/10.1039/C3SC53187BThe synthesis of meridional and facial isomers of tris-cyclometalated Pt(IV) complexes, [Pt(C^N)3]OTf, where C^N is a C-deprotonated 2-phenylpyridine-based ligand or 1-phenylpyrazole, is reported for the first time. The facial isomers exhibit high-energy emissions from essentially 3LC excited states, characterized by lifetimes of hundreds of microseconds and quantum yields up to 0.49 at room temperature in fluid solution, the highest ever found for Pt(IV) complexes. Stern–Volmer studies demonstrate the high sensitivity of the facial isomers toward oxygen and their electrochemical characterization reveals large redox gaps and a strong oxidizing character in the excited state

Organometallic Complexes of Palladium(II) Derived from 2,6- Diacetylpyridine Dimethylketal

©2010. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ This document is the Accepted version of a Published Work that appeared in final form in Organometallics. To access the final edited and published work see https://doi.org/10.1021/om100079xPdCl2 reacts with 2,6-diacetylpyridine (dap) (1 : 1) in refluxing MeOH to give the pincer complex [Pd(O1,N1,C1-L)Cl] (1) and (QH)2[PdCl2(-Cl)}]2 (2), where L is the monoanionic ligand resulting from the deprotonation of the acetyl methyl group of the monoketal of dap and QH is C5H3NHC(OMe)2Me2-2,6, the diketal of Hdap+. Reaction of 2 with NEt3 (1:2) in MeOH affords the diketal of dap, Q = C5H3NC(OMe)2Me}2-2,6 (3). Complex 1 reacts with two equiv of RNC at 0 ºC to give trans-[Pd(C1-L)Cl(CNR)2] (R = Xy (4a), tBu (4b)) but at room temperature affords [Pd(O2,C2-LR)Cl(CNR)] (R = Xy (5a), tBu (5b)). The ligand LR results from the insertion of one isocyanide into the Pd–C bond plus a tautomerization process from ketoimine to -ketoenamine, and coordinates in 5 through the carbonyl oxygen atom (O2) and the inserted isocyanide carbon atom (C2). The reaction of 1 with one equiv of RNC at 0 ºC leads a mixture of [Pd(N1,C1-L)Cl(CNR)] (R = Xy (6a), tBu (6b); 8590%), 1 and 4, but at room temperature gives the pincer complex [Pd(O1,N1,C2-LR)Cl] (R = Xy (7a), tBu (7b)) resulting from the same insertion/tautomerization processes that lead to 5. Complex 7 reacts at 0 ºC (1) with 2 equiv of RNC to give trans-[Pd(C2LR)Cl(CNXy)2] (R = Xy (8a), tBu (8b)) or (2) with one equiv of tBuNC to afford 5b. The reaction of 1 (1) with [Tl(acac)] gives [Pd(N1,C1-L)(acac)] (9), (2) with chelating ligands L^L affords [Pd(C1-L)Cl(N^N)] (N^N = 2,2’-bipyridine = bpy (10), 4,4’-di-tertbutyl-2,2’-bipyridine = dbbpy (11)), (3) with one equiv of PPh3 gives, in the same way as with isocyanides, an equilibrium mixture of [Pd(N1,C1-L)Cl(PPh3)] (12), 1 and trans[Pd(C1-L)Cl(PPh3)2] (13), which is the only product when two equiv of PPh3 is added to the reaction mixture, and (4) with excess of PPh3 affords the monoketal of dap, C5H3NC(O)Me-2}C(OMe)2Me-6} (14) and [Pd(PPh3)4]. The crystal structures of complexes 1, 2, 5b, 6a and 7a have been determined

Ru-Catalyzed C-H Arylation of Fluoroarenes with Aryl Halides

We gratefully acknowledge the Engineering and Physical Sciences Research Council (EPSRC, EP/I038578/1 and EP/ K039547/1) for funding and the European Research Council for a Starting Grant (to I.L.).

Estudios de lingüística clínica

La lingüística clínica desarrolla una función descriptiva de la patología verbal, una función interpretativa de la conducta verbal patológica y de los procesos cognitivos subyacentes y una función rehabilitadora ajustada a los diferentes tipos de deficiencia verbal. A estos objetivos hay que añadir la función que la orientación clínica puede cumplir para la propia lingüística teórica. Las orientaciones aplicadas de la lingüística (y de otras disciplinas) constituyen el terreno ineludible en el que las aproximaciones teóricas al lenguaje deben someterse a crítica y, cuando ello se hace necesario, reformularse. En los artículos que contiene esta obra se encuentran representadas, en mayor o menor medida, las diferentes funciones que acabamos de atribuir a la lingüística clínica

Structure–activity relationship studies of the phytotoxic properties of the diterpenicmoiety of breviones

Brevianes are a family of bioactivemeroterpenoids originally described in fungi of the family Penicillium. These compounds have attracted a great deal of interest not only because of their unusual skeleton, suggesting a mixed mevalonate and polyketide biogenetic pathway, and their unusual oxa-spiro ring fused to an -pyrone, but also because of the bioactivities shown bymanymembers of this family. During the course of a project aimed at the total synthesis of natural breviones A to E, the authors were able to synthesise the diterpenic moiety of brevianes and abeo-brevianes. As a result, a collection of 25 compounds were synthesised and tested for bioactivity by two different bioassays. The bioassays used were etiolated wheat coleoptiles (Triticum aestivum) and seedlings in petri dishes. The plant species tested in the seedling bioassaywere the commercial dicots lettuce and cress and themonocot weeds Echinochloa crus-galli and Lolium rigidum. The results clearly show that expanded phenanthrene-like compounds corresponding to the diterpenicmoiety of abeo-brevianes are more selective towards E. crus-galli in comparison with L. rigidum. Such selectivity can reach up to one order ofmagnitude (200-fold) andmakes someof the compoundsgood candidates as leads for the development of more specific herbicides

Handover of Patients From Prehospital Emergency Services to Emergency Departments: A Qualitative Analysis Based on Experiences of Nurses

Background: During the transfer of patients, both ambulance and hospital emergency service professionals need to exchange necessary, precise, and complete information for an effective handover. Some factors threaten a quality handover such as excessive caseload, patients with multiple comorbidities, limited past medical history, and frequent interruptions. Purpose: To explore the viewpoint of nurses on their experience of patient handovers, describing the essential aspects of the process and areas for improvement, and establishing standardized elements for an effective handover. Methods: A qualitative research method was used. Results: Nurses identified the need to standardize the patient transfer process by a written record to support the verbal handover and to transmit patient information adequately, in a timely manner, and in a space free of interruptions, in order to increase patient safety. Conclusions: An organized method does not exist. The quality of handovers could be enhanced by improvements in communication and standardizing the process

The two pion decay of the Roper resonance

We evaluate the two pion decay of the Roper resonance in a model where explicit re-scattering of the two final pions is accounted for by the use of unitarized chiral perturbation theory. Our model does not include an explicit $\epsilon$ or $\sigma$ scalar-isoscalar meson decay mode, instead it generates it dynamically by means of the pion re-scattering. The two ways, explicit or dynamically generated, of introducing this decay channel have very different amplitudes. Nevertheless, through interference with the other terms of the model we are able to reproduce the same phenomenology as models with explicit consideration of the $\epsilon$ meson.Comment: 17 latex pages, 11 eps figures. A few misprints corrected. A few new references. Version accepted for publication in Phys. Rev.