Network coevolution drives segregation and enhances Pareto optimal equilibrium selection in coordination games

In this work we assess the role played by the dynamical adaptation of the interactions network, among agents playing Coordination Games, in reaching global coordination and in the equilibrium selection. Specifically, we analyze a coevolution model that couples the changes in agents' actions with the network dynamics, so that while agents play the game, they are able to sever some of their current connections and connect with others. We focus on two update rules: Replicator Dynamics (RD) and Unconditional Imitation (UI). We investigate a Pure Coordination Game (PCG), in which choices are equivalent, and on a General Coordination Game (GCG), for which there is a risk-dominant action and a payoff-dominant one. The network plasticity is measured by the probability to rewire links. Changing this plasticity parameter, there is a transition from a regime in which the system fully coordinates in a single connected component to a regime in which the system fragments in two connected components, each one coordinated on a different action (either if both actions are equivalent or not). The nature of this fragmentation transition is different for different update rules. Second, we find that both for RD and UI in a GCG, there is a regime of intermediate values of plasticity, before the fragmentation transition, for which the system is able to fully coordinate in a single component network on the payoff-dominant action, i. e., coevolution enhances payoff-dominant equilibrium selection for both update rules.Comment: 13 pages, 8 figures, submitted to Scientific Report

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

Rhodium and Iridium complexes with a new scorpionate phosphane ligand

A straightforward synthesis of a new hybrid scorpionate ligand [(allyl)2B(CH2PPh2)(Pz)]− ([A2BPN]−) is reported. Coordination to rhodium resulted in square-planar complexes [Rh(κ2-A2BPN)(L)(L′)] [L = L′ = 1/2cod (1,5-cyclooctadiene), CNtBu, CO (6); L = CO, L′ = NH3, pyridine, PPh3, PMe3] for which spectroscopic data and the molecular structure of [Rh(κ2-A2BPN)(CO)PPh3] (11) indicate the ligand to be κN,κP-bound to rhodium with two dangling free allyl groups. Studies in solution point out that the six-membered Rh–N–N–B–C–P metallacycle undergoes a fast inversion in all of them. The bis(carbonyl) complex 6 easily loses a CO group to give [{Rh(A2BPN)(CO)}2], a dinuclear compound in which two mononuclear subunits are brought together by two bridging allyl groups. Coordination to iridium is dominated by a tripodal κN,κP,η2-C═C binding mode in the TBPY-5 complexes [Ir(κ3-A2BPN)(L)(L′)] [L = L′ = 1/2cod (3), CNtBu (5), CO (7); L = CO, L′ = PPh3 (13), PMe3 (14), H2C═CH2, (17), MeO2CC≡CCO2Me (dmad, 18)], as confirmed by the single-crystal structure determination of complexes 3 and 18. A fast exchange between the two allyl arms is observed for complexes having L = L′ (3, 5, and 7), while those having CO and L ligands (14, 17, and 18) were found to be nonfluxional species. An exception is complex 13, which establishes an equilibrium with the SP-4 configuration. Protonation reactions on complexes 13 and 14 with HCl yielded the hydride complex [Ir(κ2-A2BPN)(CO)(Cl)(H)PPh3] (15) and the C-alkyl compound [Ir{κ3-(allyl)B(CH2CHCH3)(CH2PPh2)(Pz)}(Cl)(CO)PMe3] (16), respectively. The bis(isocyanide) complex 5 reacts with dmad to form [Ir(κ2-A2BPN)(CNtBu)2(dmad)]. On the whole, the electronic density provided to the metal by the [A2BPN]− ligand is very sensitive to the coordination mode. The basicity of the new ligand is similar to that of the TpMe2 ligand in the κN,κP mode but comparable to Tp if coordinated in the κN,κP,η2-C═C mode.This research was supported by the MICINN/FEDER (Project CTQ2011-22516, Spain), Gobierno de Aragón (GA)/FSE (E70), and GA-La Caixa (Grant 2012/GA LC 057). A.L.S. thanks MICINN/FEDER for a fellowship.Peer Reviewe

Network coevolution drives segregation and enhances Pareto optimal equilibrium selection in coordination games

In this work we assess the role played by the dynamical adaptation of the interactions network, among agents playing Coordination Games, in reaching global coordination and in the equilibrium selection. Specifically, we analyze a coevolution model that couples the changes in agents’ actions with the network dynamics, so that while agents play the game, they are able to sever some of their current connections and connect with others. We focus on two action update rules: Replicator Dynamics (RD) and Unconditional Imitation (UI), and we define a coevolution rule in which, apart from action updates, with a certain rewiring probability p, agents unsatisfied with their current connections are able to eliminate a link and connect with a randomly chosen neighbor. We call this probability to rewire links the ‘network plasticity’. We investigate a Pure Coordination Game (PCG), in which choices are equivalent, and on a General Coordination Game (GCG), for which there is a risk-dominant action and a payoff-dominant one. Changing the plasticity parameter, there is a transition from a regime in which the system fully coordinates on a single connected component to a regime in which the system fragments in two connected components, each one coordinated on a different action (either if both actions are equivalent or not). The nature of this fragmentation transition is different for different update rules. Second, we find that both for RD and UI in a GCG, there is a regime of intermediate values of plasticity, before the fragmentation transition, for which the system is able to fully coordinate on a single component network on the payoff-dominant action, i.e., coevolution enhances payoff-dominant equilibrium selection for both update rules

Early (Ti, Zr)-late (Rh, Ir) heteronuclear complexes with bridging sulphido ligands

[EN]: We report in this account on the controlled synthesis of novel d0-d8 early-late heteropolynuclear diolefin and carbonyl clusters. The synthetic approach was based on additive-deprotonation reactions involving the titanium and zirconium bis-hydrosulphido complexes of formula [Cp2Ti(SH)2] and [Cptt 2Zr(SH)2] and appropriate rhodium and iridium diolefin and carbonyl compounds. The significant differences between the resulting early-late complexes and their structures coming from the titanium or zirconium metalloligand precursors are highlighted. The catalytic activity of some representative titanium-rhodium and zirconium-rhodium compounds towards alkene hydroformylation was explored. Interestingly, the heterotetranuclear 'CpTi(μ3-S)3Rh3' structure was maintained as such under mild conditions.[FR]: Nous rapportons dans cet article la préparation contrôlée de nouveaux clusters hétéropolynucléaires early-late d0–d8 portant les ligands oléfine et carbonyle. La réaction de déprotonation–addition a été la méthode de synthèse utilisée et implique la condensation de complexes bis-hydrogénosulfure du titane et du zirconium, de formule [Cp2Ti(SH)2] et [Cptt2Zr(SH)2], sur les composés adéquats du rhodium et de l’iridium portant les ligands oléfine et carbonyle. Les différences significatives de structure entre les complexes early-late ainsi préparés, dues à la nature du métalloligand précurseur du titane ou du zirconium employé, sont mises en évidence. L’activité catalytique de quelques composés représentatifs titane–rhodium et zirconium–rhodium dans l’hydroformylation d’alcènes a été mesurée. Il convient de noter que la structure hétérotétranucléaire « CpTi(μ3-S)3Rh3 » est maintenue comme telle sous des conditions douces de réaction.Peer Reviewe

Synthesis of paramagnetic tetranuclear rhodium and iridium complexes with the 2,6-pyridinedithiolate ligand. Redox-induced degradation to diamagnetic triiridium compounds

The tetranuclear complexes [M4(μ-PyS2)2(diolefin)4] [PyS2 = 2,6-pyridinedithiolate; M = Rh, diolefin = cod (1,5-cyclooctadiene) (1), tfbb (tetrafluorobenzo[5,6]bicyclo[2.2.2]octa-2,5,7-triene) (2); M = Ir, diolefin = cod (3), tfbb (4)] exhibit two one-electron oxidations at a platinum disk electrode in dichloromethane at potentials accessible by chemical reagents. The rhodium tetranuclear complexes were selectively oxidized to the monocationic complexes [Rh4(μ-PyS2)2(diolefin)4] + (1+, 2+) by mild one-electron oxidants such as [Cp2Fe]+ or [N(C6H4Br-4)3]+ and isolated as the PF6 -, BF4 -, and ClO4 - salts. Silver salts behave as noninnocent one-electron oxidants for the reactions with the rhodium complexes 1 and 2 since they give sparingly soluble coordination polymers. The complex [Ir4(μ-PyS2)2(cod)4] + (3+) was obtained as the tetrafluoroborate salt by reaction of 3 with 1 molar equiv of AgBF4, but the related complex 4+ could not be isolated from the chemical oxidation of [Ir4(μ-PyS2)2(tfbb)4] (4) with AgBF4. Oxidation of 3 and 4 with 2 molar equiv of common silver salts resulted in the fragmentation of the complexes to give the diamagnetic triiridium cations [Ir3(μ-PyS2)2(diolefin)3] +. The molecular structure of [Ir3(μ-PyS2)2(cod)3]BF 4, determined by X-ray diffraction methods, showed the three metal atoms within an angular arrangement. Both 2,6-pyridinedithiolate tridentate ligands bridge two metal-metal bonded d7 centers in pseudo octahedral environments and one d8 square-planar iridium center. An interpretation of the EPR spectra of the 63-electron mixed-valence paramagnetic tetranuclear complexes suggests that the unpaired electron is delocalized over two of the metal atoms in the complexes 1+-3+.The generous financial support from Dirección General de Enseñanza Superior e Investigación (DGES) (Projects PB98-641 and PB94-1186), and a fellowship (M. A. Casado) are gratefully acknowledged.Peer Reviewe

Cambios en el panorama televisivo español: ¿Hacia qué modelo nos encaminamos?

El presente artículo repasa la evolución legislativa española en el terreno audiovisual hasta la reciente aprobación de la Ley General de la Comunicación Audiovisual. El texto analiza la influencia del nuevo marco en el mercado televisivo en tres aspectos fundamentales: el pluralismo, la concentración y la contribución a la producción audiovisual, con vistas a su incidencia en el modelo audiovisual español y, más específicamente, el desarrollo de la televisión de pago. Del examen de este proceso los autores extraen un notable retroceso en estas materias.This paper reviews the legal Spanish evolution in the audiovisual context till the approval of the new Communication Act. The text analyses the effect of this new framework in the television market from three main perspectives: pluralism, concentration and audiovisual production, in regard to their influence in the audiovisual Spanish model and the development of pay TV. The authors observe some important backward movements from the study of this process.Publicad

Estado de salud y demanda de servicios de salud de la población ecuatoriana en España

Análisis del estado de salud y del grado de acceso a los servicios de salud de los inmigrantes ecuatorianos en la provincia de Alicante. La finalidad es descriptiva y práctica: realizar un diagnóstico comunitario de salud básico y una aproximación al nivel de demanda de los servicios sanitarios. El análisis se centra en la evaluación de la hipótesis del inmigrante sano, pero vulnerable, y en el tipo de consumo de servicios de salud realizado. Para valorar esta hipótesis se ha procedido a comparar los datos obtenidos en una encuesta a población ecuatoriana residente en la provincia de Alicante, con los de la última Encuesta Nacional de Salud 2003 y el PHOGUE (2000). Los resultados indican que el estado de salud de la población ecuatoriana es similar al de la población española que participa en el mismo mercado de trabajo que la inmigración económica (trabajadores con baja cualificación), aunque se observan algunos elementos de vulnerabilidad (en especial, en términos de salud emocional).La presente investigación ha sido financiada por el Instituto de Salud Carlos III, ref. PI042287