In honour of the 70th birthday of Professor Luis A. Oro

EssayWhen Professor Luis Oro turns over the middle of June, he will be 70 years old, and he will be completing a cycle of almost half a century (48 years) dedicated to chemical research in the field of organometallics and homogeneous catalysis, and in general to the development of chemistry. In this aim, he has assumed different and complementary responsibilities, from leading innovative research projects, to the formation of professional scientists for academia or the chemical industry, from the direction of the Spanish Royal Society of Chemistry, to that of diverse editorial management consortia or even having taken the responsibility of guiding the overall Spanish scientific policy. It has been a long trek done with tons of enthusiasm, excellent companions and plenty of generosity. It is our pleasure and privilege to walk around the main steps of Professor Oro’s life; a life dedicated to investigate and to work to situate chemical research, and science in general, in the proper place it should be in our modern society.Peer Reviewe

Approximations to an integrated model of eating disorders and muscle dysmorphia among university male students in Argentina

Male body dissatisfaction has been associated with drive for muscularity and, in extreme cases, with the clinical condition referred to as muscle dysmorphia (MD). Although recent research suggests that MD is closely linked to eating disorders (EDs), it is classed as a subtype of body dysmorphic disorder. A cross-sectional study was conducted among 402 university male students in Buenos Aires to examine common factors in the development of EDs and MD. Multiple regression analyses were performed to assess the predictive value of the investigated variables. For both conditions, the models accounted for 48 percent of the variance and were predicted by a similar set of variables. The results support the inclusion of MD within the EDs spectrum

Intervención en hombres penados por violencia de género en medidas alternativas en el Centro de Inserción Social "Trece Rosas"

Este proyecto está basado en las prácticas realizadas en el Centro de Inserción Social "Trece Rosas" de Zaragoza, en las cuales se trabaja con hombres en régimen de libertad, pero condenados por un delito de Violencia de Género, en este caso, a unas sesiones psicoeducativas como pena sustitutiva de penas privativas de libertad. A su vez, se abordan materias, como los Trabajos en Beneficio de la Comunidad (TBC), y se hace un breve recorrido en base a la legislación vigente en materia de Violencia de Género

Rhodium(I) complexes with hemilabile phosphines: Rational design for efficient oxidative amination catalysts

13 páginas, 10 figuras, 6 tablas, 4 esquemas.A series of cationic square-planar rhodium(I) complexes of type [Rh(cod){Ar2P(CH2)nZ}]+, [Rh(cod){Ar2P(CH2)nZ}2]+, and [Rh{Ar2P(CH2)nZ}2]+, which contained diverse functionalized hemilabile phosphine ligands of type Ar2P(CH2)nZ (n=1–3; Z=OMe, OEt, OnBu, NMe2, SMe), were synthesized and spectroscopically characterized. The crystal structures of representative compounds were determined by X-ray diffraction. Most complexes were active catalysts for the anti-Markovnikov oxidative amination of styrene with piperidine to produce (E)-1-styrylpiperidine. Catalyst screening showed a remarkable relationship between the hemilabile ligand, the precatalyst structure, and the catalytic activity. The more-efficient catalysts were those that had arylphosphine ligands with a 2-alkoxyethyl- or 3-alkoxypropyl hemilabile moiety, Ar2P(CH2)nOR (n=2, 3; R=Me, Et, nBu). This study has revealed the outstanding catalytic activity of bis-phosphine complexes [Rh{(4-R-C6H4)2P(CH2)3OEt}2][PF6] (R=H, Me, OMe), with unprecedented turnover frequencies of up to 80 h−1 (R=Me) and excellent enamine selectivity (96 %).Financial support from the Ministerio de Ciencia e Innovación (MICINN/FEDER): CTQ2010-15221, MULTICAT (CSD2009-00050), and Factoría de Cristalización (CSD2006-0015) is gratefully acknowledged. M.I.B. thanks the Spanish MICINN and the IUCH (Instituto Universitario de Catálisis Homogénea) for a predoctoral fellowship.Peer reviewe

Tetranuclear [Rh4(μ-PyS2) 2(diolefin)4] complexes as building blocks for new inorganic architectures: Synthesis of coordination polymers and heteropolynuclear complexes with electrophilic d8 and d10 metal fragments

The reaction of [Rh4(μ-PyS2)2(cod) 4] (PYS2 = 2,6-pyridinedithiolate, cod = 1,5-cyclooctadiene) with CF3SO3Me gave the cationic complex [Rh4(μ-PyS2Me)2(cod) 4][CF3SO3]2 (1) with two 6-(thiomethyl)pyridine-2-thiolate bridging ligands from the attack of Me+ at the terminal sulfur atoms of the starting material. Under identical conditions [Rh4(μ-PyS2)2(tfbb)4] (tfbb = tetrafluorobenzobarrelene) reacted with CF3SO3Me to give the mixed-ligand complex [Rh4(μ-PyS2)(μ-PyS 2Me)(tfbb)4][CF3SO3] (2). The nucleophilicity of the bridging ligands in the complexes [Rh4(μ -PyS2)2(diolefin)4] was exploited to prepare heteropolynuclear species. Reactions with [Au(PPh3)(Me 2CO)][ClO4] gave the hexanuclear complexes [(PPh 3)2Au2Rh4(μ-PyS2) 2(diolefin)4][ClO4]2 (diolefin = cod (3), tfbb (4)). The structure of 4, solved by X-ray diffraction methods, showed the coordination of the [Au(PPh3)]+ fragments to the peripheral sulfur atoms in [Rh4(μ-PyS2) 2(diolefin)4 along with their interaction with the neighbor rhodium atoms. Neutral coordination polymers of formula [CIMRh 4(μ-PyS2)2(diolefin)4] n (M = Cu (5, 6), Au (7)) result from the self-assembly of alternating [Rh4(μ-PyS2)2(diolefin) 4] ([Rh4]) blocks and MCI linkers. The formation of the infinite polymetallic chains was found to be chiroselective for M = Cu; one particular chain contains exclusively homochiral [Rh4] complexes. Cationic heterometallic coordination polymers of formula [MRh 4(μ-PyS2)2(diolefin)4] n (M = Ag (8, 9), Cu (10, 11)) and [Rh5(μ-PyS 2)2(diolefin)5]n[BF 4]n (12, 13) result from the reactions of [Rh 4] with [Cu(CH3CN)4]BF4, AgBF 4, and [Rh(diolefin)(Me2CO)2]BF4, respectively. The heterometallic coordination polymers exhibit a weak electric conductivity in the solid state in the range (1.2-2.8) × 10-7 S cm-1.The financial support from Ministerio de Ciencia y Tecnología (MCyT(DGI)/FEDER, Projects BQU2002-00074 and BQU2000-1170) is gratefully acknowledged.Peer Reviewe

Behavioural insights (BI) for childhood development and effective public policies in Latin America: A survey and a randomised controlled trial

Objectives We developed (a) a survey to investigate the knowledge of childhood health experts on public policies and behavioural insights (BI), as well as its use in Latin American and the Caribbean countries (LACs), and (b) an intervention (randomised controlled trial) to test the influence of nudges on the effect of a simulated public health programme communication. Participants and settings A total of 2003 LACs childhood health professionals participated in the study through a Hispanic online platform. Primary and secondary outcomes We used regression models analysing expertise-related information, individual differences and location. We extracted several outcome variables related to (a) ‘Public Policy Knowledge Index’ based on the participants’ degree of knowledge on childhood health public policies and (b) BI knowledge, perceived effectiveness and usefulness of a simulated public programme communication. We also analysed a ‘Behavioural Insights Knowledge Index’ (BIKI) based on participants’ performance in BI questions. Results In general, health professionals showed low BI knowledge (knowledge of the term BI: χ2 =210.29, df=1 and p<0.001; BIKI: χ2 =160.5, df=1 and p<0.001), and results were modulated by different factors (age, academic formation, public policy knowledge and location). The use of BI principles for the communication of the public programme revealed higher impact and clarity ratings from professionals than control messages. Conclusions Our findings provide relevant knowledge about BI in health professionals to inform governmental and non-governmental organisations’ decision-making processes related with childhood public policies and BI designs.Fil: Tomio, Andrea A.. Universidad de San Andrés; ArgentinaFil: Dottori, Martin. Universidad de San Andrés; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Hesse Rizzi, Eugenia Fátima. Universidad de San Andrés; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Torrente, Fernando Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Neurociencia Cognitiva. Fundación Favaloro. Instituto de Neurociencia Cognitiva; ArgentinaFil: Flichtentrei, Daniel. IntraMed; ArgentinaFil: Ibañez, Agustin Mariano. Universidad de San Andrés; Argentina. University Of California at San Francisco; Estados Unidos. Universidad de Dublin; Irlanda. Universidad Adolfo Ibañez; Chile. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentin

TRIBUNAL ARBITRAL DE ALPOPULAR ALMACÉN GENERAL DE DEPÓSITOS S.A. VS. UNIDAD ADMINISTRATIVA ESPECIAL - DIRECCIÓN DE IMPUESTOS Y ADUANAS NACIONALES (DIAN)

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The anions [Cptt2Zr(μ-S)2M(CO)2]- (M = Rh, Ir) as versatile precursors for the synthesis of sulfido-bridged early−late heterotrimetallic (ELHT) compounds

The reaction of [Cp2 ttZr(μ3-S) 2{Ir(CO)2}2] (Cptt = η5-1,3-di-tert-butylcyclopentadienyl) with dppe (1,2-bis-(diphenylphosphino)ethane) affords the ion-pair compound [Ir(CO)(dPPe)2][Cp2 ttZr(μ-S) 2Ir(CO)2] (2). The related compound [Rh(dPPe) 2][Cp2 ttZr(μ-S)2Rh(CO) 2] (5) has been obtained in solution under a carbon monoxide atmosphere by reaction of [Cp2 ttZr(μ3-S) 2{Rh(CO)2}2] with dppe through the intermediate heterotrinuclear compound [Cp2 ttZr(μ3-S) 2{Rh(dppe)}{Rh(CO)2}] (4). Reaction of the heterodinuclear anion [Cp2 ttZr(μ-S)2Ir(CO) 2]-, generated in situ, with [Rh(μ-Cl)(cod)] 2, [RhCl2(CO)2]- and [Pd(μ-Cl)-(η3-C3H5)]2 affords the d0-d8-d8 early-late compounds [Cp 2 ttZr(μ3-S)2{Ir(CO) 2}{Rh(cod)}] (6), [Cp2 tt-Zr(μ3-S) 2{Ir(CO)2}{Rh(CO)2}] (7), and [Cp 2 ttZr(μ3-S)2{Ir(CO) 2}{Pd(η3-C3H5)}] (8) each with a symmetrical trigonal-bipyramidal M3(μ3-S)2 heterotrimetallic metal-sulfur core. In the same way, the reaction of [Cp 2 ttZr(μ-S)2M(CO)2]- (M = Rh, Ir) with [AuCl(PPh3)] leads to the preparation of the d 0-d8-d10 early-late compounds [Cp 2 ttZr(μ-S)2(Ir(CO)2}{Au(PPh 3)}] (9) and [Cp2 ttZr(μ-S) 2{Rh(CO)2}{Au(PPh3)}] (10) with an open M 3(μ3-S)(μ2-S) heterotrimetallic metal-sulfur framework. On the other hand, treatment of the bis(hydrosulfido) zirconium compound [Cp2 ttZr(SH)2] with triethylamine followed by addition of [Pd(μ-Cl)(η3-C 3H5)]2 or [AuCl(PPh3)] affords the sulfido-bridged early-late heterobimetallic compounds [Cp2 ttZr(μ3-S)2{Pd(η3-C 3H5)}2] (11) and [Cp2 ttZr(μ-S)2(Au(PPh3)}2] (12). The molecular structure of complexes 9 and 12 determined by X-ray diffraction methods are also described.The financial support from Ministerio de Educación y Ciencia (MEC/FEDER) is gratefully acknowledged (Projects CTQ2006-03973/BQU and Factoría de Cristalización, CONSOLIDER INGENIO-2010).Peer Reviewe

Synthesis of tetranuclear rhodium and iridium complexes directed by 6-mercaptopyridin-2-ol: Electrochemical behavior, chemical oxidation, and coordination chemistry

The new ligand 6-mercapto-2(1 H)-pyridone (H2PySO) has been prepared in good yield by reaction of 6-chloro-pyridin-2-ol with NaSH. Reaction of the salt K2PySO, generated in situ, with the appropriate complex [M(μ-C1)(diolefin)]2affords the tetranuclear complexes [M 4(μ-PySO)2(diolefin)4] [M = Rh, diolefin = 1,5-cyclooctadiene (cod) (1), tetrafluorobenzobarralene (tfbb) (2); M = lr, diolefin = cod (3)]. The molecular structure of complex 1 has been determined by X-ray diffraction methods. The tetranuclear structure is supported by two S, N, Otridentate ligands exhibiting a 1κO, 2κN, 3:4κ2 S coordination mode. Carbonylation of the rhodium diolefin complexes at atmospheric pressure gives [Rh4(μ-PyS0)2(C0)8] (4). The carbonylation of 1 is partially reversible, and the mixed-ligand complex [Rh4(μ-PySO)2(cod)2(CO)4] (5) has been obtained as a single isomer. The reaction of 4 with triphenylphosphine gives the compound [Rh4(μ-PySO)2(CO)4(PPh 3)4] (6) which also exists as a single isomer of C 2 symmetry. The diolefin complexes are redox active and exhibit two one-electron oxidations at a platinum disk electrode in dichloromethane separated by approximately 0.5 V at potentials accessible by chemical oxidants. The tetranuclear complexes were selectively oxidized to the 63-electron mixed-valence cationic complexes [M4(μ-PySO)2(diolefin) 4]+(1a+, 2+, and 3+) by using AgCF3SO3 as oxidant and isolated as the triflate salts. Alternatively, the oxidation with [Cp2Fe]PF6 gives [Rh4(μ-PySO)2(cod)4][PF6] (1b+). The parameters obtained from the simulation of the electron paramagnetic resonance spectra of the oxidized species strongly suggest that the unpaired electron is delocalized over only two metal atoms in the complexes.The financial support from Ministerio de Educación y Ciencia (MEC/FEDER) Project CTQ2006-03973/BQU and Grant CSD2006-0015 Consolider Ingenio 2010 is gratefully acknowledged.Peer Reviewe

Synthesis of titanium and zirconium complexes with 2-pyridonate and 2, 6-pyridinedithiolate ligands

Special Issue: Dedicated to Professor F. Ekkehardt Hahn on the Occasion of His 60th Birthday with our most Sincere Congratulations for his Outstanding Contributions to Chemistry and Best Wishes.Treatment of complex [Cp2TiCl2] with the lithium salt of 2-hydroxypyridine afforded complex [Cp2Ti(Opy)2] (1), whereas the same synthetic strategy applied to the analogous zirconium compound [Cp2ZrCl2] did not worked. However, the use of the metallocene [Cptt 2ZrMe2] with protic ligands allowed directing the reactivity towards protonation of the methyl groups attached to zirconium. To check this approach we reacted [Cptt 2ZrMe2] with methanol affording complex [Cptt 2ZrMe(OMe)] (2), which was characterized in situ by NMR techniques. In the same line, the reaction of [Cptt 2ZrMe2] with 2-hydroxypyridine gave complex [Cptt 2Zr(Me)(Opy)] (3); forcing the conditions of this reaction did not lead to the expected complex [Cptt 2Zr(Opy)2], most probably due to the steric hindrance exerted by the bulky cyclopentadienyl ligands. Further reactions of complex 3 with ligands having acidic protons also led to the recovery of the starting complex. However, when shifting to the bifunctional ligand 2, 6-dimercaptopyridine [py(SH)2] a double protonation of the methyl ligands in [Cptt 2ZrMe2] occurred, allowing the isolation of mononuclear complex [Cptt 2Zr(κS,κS,κN-pyS2)] (4), upon evolution of methane. The molecular structure of complex 4 was determined by X-ray methods, showing the zirconium atom in a highly distorted trigonal bipyramidal arrangement; structural parameters indicate a conventional Zr-N bond, but rather weak Zr-S interactions.Financial support from the Spanish Ministry of Economy and Competitiveness (MINECO/FEDER, Projects CTQ2012-35665 and CTQ2013-42532-P), MICINN (Project Consolider Ingenio 2010, CSD2009-00050) and Diputación General de Aragón (DGA/ FSE-E07 and E70) is gratefully acknowledged.Peer Reviewe