Synthesis and reactivity of half-sandwich (η 5 -C 5 Me 5 )Ir(iii) complexes of a cyclometallated aryl phosphine ligand

Reaction of the Ir(iii) dimer [(η 5 -C 5 Me 5 )IrCl 2 ] 2 with PMeXyl 2 (Xyl = 2,6-C 6 H 3 Me 2 ), in the presence of the poorly coordinating base 2,2,6,6-tetramethyl piperidine, gives a chloride complex 1-Cl, resulting from hydrogen chloride elimination involving one of the phosphine benzylic hydrogen atoms and concomitant cyclometallation. Related compounds containing other halide or pseudohalide ligands, 1-Br, 1-Cl, 1-SCN, can be made, the latter featuring S-coordination of the ambidentate thiocyanate to the soft Ir(iii) Lewis acid centre, as suggested by IR data and demonstrated by X-ray crystallography. Hydride 2-H, and alkyl derivatives 3 (Me) and 4 (CH 2 SiMe 3 ) can also be prepared from 1-Cl and appropriate hydride and alkylating reagents. An interesting H/D exchange chemistry that occurs in the presence of CD 3 OD has been disclosed for 1-Cl, 1-Br and 2-H. For the halide derivatives, deuterium incorporation takes place into the methylene and methyl sites of their cyclometallated ligand, whereas for 2-H only the hydride and methylene (Ir-CH 2 ) protons participate in the exchange, which is strikingly accelerated by catalytic amounts of acids.Ministerio de Ciencia e Innovación CTQ2010-17476Consolider-Ingenio2010 CSD2007-0000Junta de Andalucia FQM-119, P09-FQM-483

Reactivity of a trans-[H-Mo≣Mo-H] Unit Towards Alkenes and Alkynes. Bimetallic Migratory Insertion, H-Elimination and Other Reactions

Complex [Mo2(H)2{μ-HC(NDipp)2}2(THF)2], (1·THF), reacts with C2H4 and PhCH[double bond, length as m-dash]CH2 to afford hydrido-hydrocarbyl and bis(hydrocarbyl) derivatives of the Mo[quadruple bond, length as m-dash]Mo bond. Reversible migratory insertion and β-hydrogen elimination, as well as reductive elimination and other reactions, have been uncovered. PhC[triple bond, length as m-dash]CH behaves instead as a Brönsted–Lowry acid towards the strongly basic Mo–H bonds of 1·THF.Ministerio de Economía y Competitividad CTQ2016-75193-PEuropean Research Council 75657

Large-scale preparation and labelling reactions of deuterated silanes

A catalytic synthesis of deuterated silanes SiEt3D, SiMe2PhD and SiPh2D2 is reported that allows their facile generation in a 3–4 g scale, utilizing D2 (0.5 bar) as the hydrogen isotope source and low catalyst loadings (0.01 mol%). The catalyst precursor is the rhodium (III) complex 1, which contains a (η5‐C5Me5)Rh cation stabilized by coordination to a cyclometallated phoshine PMeXyl2 (Xyl = 2,6‐C6H3Me2). The same complex is also an active catalyst for the hydrosilylation of the CO and C≡N bonds of various ketones, aldehydes and α,β‐unsaturated nitriles. Hence, combination of these two properties permits development of a simple and proficient one‐flask, two‐step procedure for the deuterosilylation of these substrates.Ministerio de Ciencia y Tecnología CTQ2010‐17476, Consolider‐Ingenio 2010 CSD2007‐00006Junta de Andalucía FQM‐119, P09‐FQM‐4832Ministerio de Educación AP20080256CONACYT (Mexico) 2293

OpenZmeter: An Efficient Low-Cost Energy Smart Meter and Power Quality Analyzer

Power quality and energy consumption measurements support providers and energy users with solutions for acquiring and reporting information about the energy supply for residential, commercial, and industrial sectors. In particular, since the average number of electronic devices in homes increases year by year and their sensitivity is very high, it is not only important to monitor the total energy consumption, but also the quality of the power supplied. However, in practice, end-users do not have information about the energy consumption in real-time nor about the quality of the power they receive, because electric energy meters are too expensive and complex to be handled. In order to overcome these inconveniences, an innovative, open source, low-cost, precise, and reliable power and electric energy meter is presented that can be easily installed and managed by any inexperienced user at their own home in urban or rural areas. The system was validated in a real house over a period of two weeks, showing interesting results and findings which validate our proposal

Coordination of LiH Molecules to Mo≣Mo Bonds: Experimental and Computational Studies on Mo2LiH2, Mo2Li2H4, and Mo6Li9H18 Clusters

The reactions of LiAlH4 as the source of LiH with complexes that contain (H)Mo≣Mo and (H)Mo≣Mo(H) cores stabilized by the coordination of bulky AdDipp2 ligands result in the respective coordination of one and two molecules of (thf)LiH, with the generation of complexes exhibiting one and two HLi(thf)H ligands extending across the Mo≣Mo bond (AdDipp2 = HC(NDipp)2; Dipp = 2,6-iPr2C6H3; thf = tetrahydrofuran, C4H8O). A theoretical study reveals the formation of Mo–H–Li three-center–two-electron bonds, supplemented by the coordination of the Mo≣Mo bond to the Li ion. Attempts to construct a [Mo2{HLi(thf)H}3(AdDipp2)] molecular architecture led to spontaneous trimerization and the formation of a chiral, hydride-rich Mo6Li9H18 supramolecular organization that is robust enough to withstand the substitution of lithium-solvating molecules of tetrahydrofuran by pyridine or 4-dimethylaminopyridine.España Ministry of Economy and Competitiveness (PID2019-110856GA-I00 and PGC2018-093863-B-C21)Generalitat de Catalunya - AGAUR (grant 2017-SGR1289

Synthesis, properties, and some rhodium, iridium, and platinum complexes of a series of bulky m-terphenylphosphine ligands

A series of sterically demanding aryl phosphine ligands (L) bearing terphenyl substituents, PR2Ar′ (R = hydrocarbyl, Ar′ = 2,6-diarylphenyl radical) has been prepared and characterized. The stability of these ligands towards oxidation in the air has been tested, and theoretical and experimental studies aimed to provide information on their electronic and steric properties have been performed. Treatment of the metal dimers [MCl(COD)]2(M = Rh, Ir; COD = 1,5-cyclooctadiene) with ligands PMe2ArXyl2(L1) and PMe2ArDipp2(L5), in a 1:1 metal:ligand ratio, afforded the expected square-planar 16-electron complexes [MCl(COD)(PMe2ArXyl2)] and [MCl(COD)(PMe2ArDipp2)], respectively. These compounds were readily converted into the corresponding dicarbonyl derivatives, [MCl(CO)2(PMe2ArXyl2)] and [MCl(CO)2(PMe2ArDipp2)], respectively. While the expected κ1-P coordination mode of the PR2Ar′ ligands is found for these rhodium and iridium species, the mononuclear Pt(II) derivative obtained by reaction of PtCl2with PMe2ArDipp2has composition [PtCl2(PMe2ArDipp2)], and exhibits a bidentate κ1-P, η1-arene coordination mode involving one of the ipso carbon atoms of a flanking terphenyl aryl ring. The corresponding carbonyl compound [PtCl2(CO)(PMe2ArDipp2)], was generated under a CO atmosphere and exhibits κ1-P coordination mode.Ministerio de Ciencia CTQ2013-42501-P, CTQ2014-51912-REDC, CTQ-2014-52769-C3-3-RJunta de Andalucía FQM-119 P09-FQM-4832, FQM-2126European Union 26722

A versatile approach to access trimetallic complexes based on trisphosphinite ligands

A straightforward method for the preparation of trisphosphinite ligands in one step, using only commercially available reagents (1,1,1-tris(4-hydroxyphenyl)ethane and chlorophosphines) is described. We have made use of this approach to prepare a small family of four trisphosphinite ligands of formula [CH3C{(C6H4OR2)3], where R stands for Ph (1a), Xyl (1b, Xyl = 2,6-Me2-C6H3), iPr (1c), and Cy (1d). These polyfunctional phosphinites allowed us to investigate their coordination chemistry towards a range of late transition metal precursors. As such, we report here the isolation and full characterization of a number of Au(I), Ag(I), Cu(I), Ir(III), Rh(III) and Ru(II) homotrimetallic complexes, including the structural characterization by X-ray diffraction studies of six of these compounds. We have observed that the flexibility of these trisphosphinites enables a variety of conformations for the different trimetallic species.European Research Council 756575Ministerio de Ciencia, Innovación y Universidades CTQ2017-92622-EX

Discovery and validation of an NMR-based metabolomic profile in urine as TB biomarker

Despite efforts to improve tuberculosis (TB) detection, limitations in access, quality and timeliness of diagnostic services in low- and middle-income countries are challenging for current TB diagnostics. This study aimed to identify and characterise a metabolic profile of TB in urine by high-field nuclear magnetic resonance (NMR) spectrometry and assess whether the TB metabolic profile is also detected by a low-field benchtop NMR spectrometer. We included 189 patients with tuberculosis, 42 patients with pneumococcal pneumonia, 61 individuals infected with latent tuberculosis and 40 uninfected individuals. We acquired the urine spectra from high and low-field NMR. We characterised a TB metabolic fingerprint from the Principal Component Analysis. We developed a classification model from the Partial Least Squares-Discriminant Analysis and evaluated its performance. We identified a metabolic fingerprint of 31 chemical shift regions assigned to eight metabolites (aminoadipic acid, citrate, creatine, creatinine, glucose, mannitol, phenylalanine, and hippurate). The model developed using low-field NMR urine spectra correctly classified 87.32%, 85.21% and 100% of the TB patients compared to pneumococcal pneumonia patients, LTBI and uninfected individuals, respectively. The model validation correctly classified 84.10% of the TB patients. We have identified and characterised a metabolic profile of TB in urine from a high-field NMR spectrometer and have also detected it using a low-field benchtop NMR spectrometer. The models developed from the metabolic profile of TB identified by both NMR technologies were able to discriminate TB patients from the rest of the study groups and the results were not influenced by anti-TB treatment or TB location. This provides a new approach in the search for possible biomarkers for the diagnosis of TB

Desafíos de las metrópolis: Efectos ambientales y sociales. Tendencias geográficas II

El libro está conformado de estudios realizados por profesores-investigadores de la Universidad Autónoma del Estado de México, de la Universidad de Varsovia, así como de la Universidad Pedagógica Comisión de Educación Nacional de Cracovia. En esta obra se exponen algunas investigaciones sobre los cambios en los factores sociales, naturales, económicos y ambientales como principales desafios que presentan las zonas de México, Polonia y de contextos de Sudamérica, tales como Sao Paulo, Quito y Bogotá y ciudades medias y pequeñas.Universidad Autónoma del Estado de Méxic

Territorios sustentables en contexto de pandemia

La obra ofrece trabajos que brindan un conocimiento científico sobre el impacto de la pandemia en la salud, la economía, el ambiente y los territorios y se plantean desafíos para hacer más sostenible la vida en las ciudades y en el campo para insertarse y poder competir a nivel global