Análisis de las empresas andaluzas que participan en los proyectos del programa europeo CORDIS

Debido a la pérdida de competitividad económica de la Unión Europea frente a países emergentes, la Comisión Europea ha decidido impulsar la innovación y el desarrollo de los países miembros mediante proyectos innovadores. Para ello, dota de financiación a organizaciones públicas y privadas que llevan a cabo proyectos de I+D, que son coordinados por el programa europeo Cordis. Con este propósito conviene realizar un trabajo de análisis e indagación para entender como funcionan estas ayudas en los países miembros de la Unión Europea, y más concretamente en la comunidad autónoma de Andalucía, además de la repercusión en la vida cotidiana y en el bienestar los ciudadanos. Veremos la influencia del desarrollo de estas políticas en la calidad de vida de la sociedad y, además, si influyen en los estándares de vida establecidos. Por todo ello, podremos obtener una explicación detallada de la repercusión de los proyectos innovadores en Andalucía, estableciendo relaciones y analizando el funcionamiento de la financiación recibida por los entes andaluces participantes en tales proyectos. Con todo esto y más, estableceremos reflexiones donde se conocerán los puntos fuertes y débiles de Andalucía respecto a la innovación y el desarrollo, además de conocer las principales oportunidades y retos asumibles en un futuro próximo. Asimismo, fijaremos conclusiones para crear una conciencia social innovadora y de mayor repercusión en la economía europea.Universidad de Sevilla. Grado en Administración y Dirección de Empresa

An efficient approach for the computation of 2-D Green's functions with 1-D and 2-D periodicities in homogeneous media

This paper presents an algorithm for the acceleration of the series involved in the computation of 2-D homogeneous Green's functions with 1-D and 2-D periodicities. The algorithm is based on an original implementation of the spectral Kummer-Poisson's method, and it can be applied to the efficient computation of a wide class of infinite series. In the algorithm the number of asymptotic terms retained in Kummer's transformation is externally controlled so that any of the series that has to be accelerated is split into one series with exponential convergence and another series with algebraic convergence of arbitrarily large order. Numerical simulations have shown that there is an "optimum" number of asymptotic terms retained in Kummer's transformation for which the CPU time needed in the summation of the series is minimized. The CPU times required by Ewald's method for the evaluation of 2-D Green's functions with 1-D and 2-D periodicities have been compared with those required by the present algorithm, and the algorithm has been found to be between 1.2 and 3 times faster than Ewald's method when working in "optimum" operation conditions.Ministerio de Educación y Ciencia TEC2007-65376Junta de Andalucía TIC-25

Copper-Induced Ammonia N-H Functionalization

The activation of ammonia has been achieved with the aid of the TpMsCu core (TpMs = hydrotris(3-mesityl-pyrazolyl)borate). Complexes of the general composition TpMsCu(amine) (1–4) including the ammonia adduct TpMsCu(NH3) (1) have been synthesized and fully spectroscopical- and structurally characterized. Coordinated ammonia in 1 has been reacted with Ph3CPF6 yielding TpMsCu(NH2CPh3) (5) as a result of N–H cleavage and N–C bond formation. In a parallel manner the catalytic functionalization of ammonia with ethyl diazoacetate leading to glycinate derivatives has been developed with TpMsCu(THF) as the catalyst, in the first example of this transformation with ammonia and a copper-based system.We thank Prof. Kurt Mereiter for helpful discussions. Support for this work was provided by the MINECO (CTQ2014-52769-C3-1-R), and the Junta de Andalucia (P10-FQM-06292). MA thanks MINECO for a FPI fellowship

Copper(I)-Arene Complexes with a Sterically Hindered Tris(pyrazolyl)borate Ligand

A series of arene copper(I) complexes bearing the hydrotris(3-mesitylpyrazolyl)borate ligand (Tp(Ms)) of general formula Tp(Ms)Cu(arene) (arene = toluene, 1; nitrobenzene, 2; chlorobenzene, 3; and iodobenzene, 4) has been structurally characterized. Complexes 1-3 show a (2)-arene coordination mode to the copper center, whereas the iodobenzene ligand in 4 is coordinated to Cu by the iodine atom. In the absence of excess arene, these compounds undergo arene loss and formation of the dinuclear complex [Tp(Ms)Cu](2) (5), which has also been structurally characterized. Given the number of catalytic systems described in which the Tp(x)Cu core plays the main role, the observation of these adducts assesses their presence in those catalytic systems, a feature not described to date.Support for this work was provided by MINECO (CTQ2014-52769-C3-1-R

The Elusive Palladium-Diazo Adduct Captured: Synthesis, Isolation and Structural Characterization of [(ArNHC-PPh2)Pd(eta(2)-N2C(Ph)CO2Et)]

The first example of a diazo palladium adduct is reported. The complexes [(ArNHC-PPh2) M(eta(N2C)-N-2(Ph) CO2Et)] (M = Ni, 3; M = Pd, 4; ArNHC-PPh2 = 3-(2,6-diisopropylphenyl)- 1-[(diphenylphosphino)ethyl] imidazol-2-ylidene) were prepared by ligand exchange with styrene-coordinated precursors [(ArNHC @ PPh2) M(styrene)] (M = Ni, 1; M = Pd, 2). Complex 4 was fully characterized, including X-ray analyses; this constitutes the first example of a diazo adduct compound with palladium, thereby closing the gap between Groups 8 and 10 regarding this type of compounds

Selective Functionalization of Arene C(sp2 )−H Bonds by Gold Catalysis: The Role of Carbene Substituents

The complete regioselective incorporation of carbene units to nonactivated arene rings has been achieved employing gold(I) catalysts bearing alkoxydiaminophosphine ligands, with readily available, nonelaborated ethyl 2-phenyl-diazoacetate as the carbene source. These results are in contrast with the scarce precedents which required highly elaborated diazo substrates. Density functional theory (DFT) calculations have revealed the important role of the R group in the C(R)CO 2Et fragment, which dramatically affects the energy profile of this transformation.We thank the Ministerio de Ciencia e Innovación for Grant PID2020-113797RB-C21, also financed by FEDER “Una manera de hacer Europa”. We also thank Junta de Andalucía (P18-RT-1536) and Universidad de Huelva (P.O. Feder UHU-1260216). I.S. and A.N. acknowledge the support from the Research Council of Norway through its FRINATEK (No. 314321), Centre of Excellence schemes (No. 262695), and the Norwegian Metacenter for Computational Science (NOTUR) for computational resources (project number nn4654k). Funding for open access charge: Universidad de Huelva / CBU

Selective C-H Bond Functionalization of Unprotected Indoles by Donor-Acceptor Carbene Insertion

Copper catalysts containing alkoxydiaminophosphine (ADAP) ligand catalyze the selective C3- H functionalization of unprotected indoles upon carbene transfer from donor-acceptor diazo compounds, the N-H bond remaining unaltered during the transformation. Mechanistic studies, including DFT calculations, allows proposing the existence of two competitive pathways, none of them occurring through the formation of cyclopropane intermediates, at variance with previously reported systems.We thank to Ministerio de Ciencia e Innovación for Grants PID2020-113797RB-C21, PID2020-112825RB-I00 and CEX2019-000925-S. We also thank Junta de Andalucía (P18-1536) and Universidad de Huelva (P. O.Feder UHU-202024). I.-G. F thanks the Investigo Program for a contract. L. M.-G. thanks Generalitat de Catalunya for an FI-Agaur predoctoral contract, 2022FI−B2000621

Mechanistic Studies on Gold-Catalyzed Direct Arene C–H Bond Functionalization by Carbene Insertion: The Coinage-Metal Effect

The catalytic functionalization of the Csp 2-H bond of benzene by means of the insertion of the CHCO2Et group from ethyl diazoacetate (N2=CHCO2Et) has been studied with the series of coinage metal complexes IPrMCl (IPr = IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene) and NaBArF 4 (BArF 4 = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate). For Cu and Ag, these examples constitute the first of such metals toward this transformation, that also provides ethyl cyclohepta-2,4,6-trienecarboxylate as by-product from the so-called Buchner reaction. In the case of methyl-substituted benzenes, the reaction exclusively proceeds onto the aromatic ring, the Csp 3-H bond remaining unreacted. A significant coinage metal effect has been observed, since the gold catalyst favors the formation of the insertion product into Csp 2-H bond whereas copper and silver preferentially induce the formation of the cycloheptatriene derivative. Experimental studies and theoretical calculations have explained the observed selectivity in terms of the formation of a common Wheland intermediate, resembling an electrophilic aromatic substitution, from which the reaction pathway evolves into two separate routes to each product.We thank the Spanish MINECO for CTQ2014-52769-C3-1-R, CTQ2014-57761-R, RED INTECAT CTQ2014-52974-REDC and Severo Ochoa Excellence Accreditation 2014-2018 SEV-2013-0319 and the ICIQ Foundation for financial support

Aerobic Intramolecular Carbon-Hydrogen Bond Oxidation Promoted by Cu(I) Complexes

The oxidation of C–H bonds by copper centres in enzymes with molecular oxygen takes place in nature under ambient conditions. Herein we report a similar transformation in which under ambient pressure and temperature (1 atm, 25 °C) the complex TpMsCu(THF) (TpMs = hydrotris(3-mesityl-pyrazol-1-yl)borate) undergoes the intramolecular oxidation of an alkylic C–H bond with O2, leading to the formation of a trinuclear compound where alkoxy and hydroxyl ligands are bonded to the copper centres, as inferred from X-ray studies. The presence of adventitious Cu(0) derived from the partial decomposition of initial TpMsCu(THF) facilitates the formation of such a trinuclear compound. DFT studies support the reaction taking place through a Cu(III) alkoxy-hydroxyl copper intermediate.Support for this work was provided by the MINECO (CTQ2017- 82893-C2-1-R CTQ2017-87889-P and CTQ2017-89132-P) and P.O. FEDER 2014-2020, UHU-1260216. MA thanks Ministerio de Economía y Competitividad for an FPI predoctoral fellowship

El potencial empresarial femenino y los factores empresariales que lo condicionan : el caso de Andalucía occidental

Este trabajo, continuación del ya publicado por las autoras sobre los factores personales que condicionan la potencialidad empresarial, (Boletín Económico de ICE, número 2754, de 2003) tiene como finalidad analizar la incidencia de otra serie de factores como son los empresariales en el surgimiento de nuevas empresarias. Como aplicación del modelo se analiza dichos factores para el caso de Andalucía occidental haciendo referencia expresa a la discriminación por género