Silver coordination polymers with tri- and hexacyanoethyl-functionalized macrocyclic ligands

Tri-and hexa-cyanoethyl functionalized 17-(L-1) and 42-membered (L-2) macrocyclic compounds were obtained by [1 + 1] (for L-1) or [2 + 2] (for L-2) cyclocondensation of the corresponding dialdehyde and diethylenetriamine, followed by hydrogenation by KBH4 and subsequent cyano-functionalization with acrylonitrile. They react with silver nitrate, leading to the formation of [AgL1](NO3) (1) and of the metalorganic coordination polymers [Ag-2(NO3)(2)L-1](n) (2) and {[Ag2L2](NO3)(2)}(n) (3). The complexes were characterized by elemental analysis, H-1 NMR, C-13 NMR, IR spectroscopies, and ESI-MS; moreover, L-2, 1, 2 and 3 were also characterized by single crystal X-ray diffraction. The metal cation in 1 is pentacoordinated with a N3O2 coordination environment; in 2, the metal cations display N4O2 octahedral and N2O3 square-pyramid coordination and in 3 they are in square-planar N-4 sites. In 1, the ligand acts as a pentadentate chelator, and in the other two cases, the ligands behave as octadentate chelators in a 1 kappa N-3:kappa O-2,2 kappa N,3 kappa N,4 kappa N (in 2) or 1 kappa N-3,2 kappa N-3,3 kappa N,4 kappa N fashion (in 3). The cyanoethyl strands of the ligands are directly involved in the formation of the 2D frameworks of 2 and 3, which in the former polymer can be viewed as a net composed of hexametallic 36-membered macrocyclic rings and in the latter generates extra hexametallic 58-membered cyclic sets that form zig-zag layers. The thermal analytical and electrochemical properties of these silver complexes were also studied.

Y Trinuclear Cu-II structural isomers coordination, magnetism, electrochemistry and catalytic activity towards the oxidation of alkanes

The reaction of the Schiff base (3,5-di-tert-butyl-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (H3L) with copper(II) nitrate, acetate or metaborate has led to the isomeric complexes [Cu-3(L)(2)(MeOH)(4)] (1), [Cu-3(L)(2)(MeOH)(2)]2MeOH (2) and [Cu-3(L)(2)(MeOH)(4)] (3), respectively, in which the ligand L exhibits dianionic (HL2-, in 1) or trianionic (L3-, in 2 and 3) pentadentate 1O,O,N:2N,O chelation modes. Complexes 1-3 were characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography, electrochemical methods and variable-temperature magnetic susceptibility measurements, which indicated that the intratrimer antiferromagnetic coupling is strong in the three complexes and that there exists very weak ferromagnetic intermolecular interactions in 1 but weak antiferromagnetic intermolecular interactions in both 2 and 3. Electrochemical experiments showed that in complexes 1-3 the Cu-II ions can be reduced, in distinct steps, to Cu-I and Cu-0. All the complexes act as efficient catalyst precursors under mild conditions for the peroxidative oxidation of cyclohexane to cyclohexyl hydroperoxide, cyclohexanol and cyclohexanone, leading to overall yields (based on the alkane) of up to 31% (TON = 1.55x10(3)) after 6 h in the presence of pyrazinecarboxylic acid.

Arylhydrazones of barbituric acid: synthesis, coordination ability and catalytic activity of their CoII, CoII/IIIand CuIIcomplexes toward peroxidative oxidation of alkanes

New ortho-substituted arylhydrazones of barbituric acid, 5-(2-(2-hydroxyphenyl)hydrazono) pyrimidine-2,4,6(1H,3H,5H)-trione (H4L1) and the sodium salt of 2-(2-(2,4,6-trioxotetra-hydropyrimidin-5(2H)-ylidene)hydrazinyl) benzenesulfonic acid (H4L2), [Na(H3L2)(mu-H2O)(H2O)(2)](2) (1), were used in the synthesis of Cu-II, Co-II and Co-II/III complexes, [Cu(H2L1)(H2O)(im)]center dot 3H(2)O (im = imidazole) (2), [Co(H2O)(6)] [Co(H2L1)(2)](2)center dot 8H(2)O (3), [Co(H2L2)(im)(3)] (4), [Cu(H2L2)(im)(2)]center dot H2O (5) and [Co(H2O)(6)][H3L2](2)center dot 8H(2)O (6). The complexes are water soluble and the mono-or di-deprotonated ligands display different coordination modes, depending on the synthetic conditions. The electrochemical behaviour of all the compounds was investigated by cyclic voltammetry and controlled potential electrolysis, revealing that the ligands are also redox active. All the compounds were evaluated as catalysts for the peroxidative (with H2O2) oxidation of cyclohexane at room temperature. The compounds 2 and 3 are the most active ones (yields up to 21% and TON up to 213 are achieved, in the presence of 3).

Novel coordination polymers with (Pyrazolato)-based tectons: catalytic activity in the peroxidative oxidation of alcohols and cyclohexane

Coupling five rigid or flexible bis(pyrazolato)based tectons with late transition metal ions allowed us to isolate 18 coordination polymers (CPs). As assessed by thermal analysis, all of them possess a remarkable thermal stability, their decomposition temperatures lying in the range of 340-500 degrees C. As demonstrated by N-2 adsorption measurements at 77 K, their Langmuir specific surface areas span the rather vast range of 135-1758 m(2)/g, in agreement with the porous or dense polymeric architectures retrieved by powder X-ray diffraction structure solution methods. Two representative families of CPs, built up with either rigid or flexible spacers, were tested as catalysts in (0 the microwave-assisted solvent-free peroxidative oxidation of alcohols by t-BuOOH, and (ii) the peroxidative oxidation of cydohexane to cydohexanol and cydohexanone by H2O2 in acetonitrile. Those CPs bearing the rigid spacer, concurrently possessing higher specific surface areas, are more active than the corresponding ones with the flexible spacer. Moreover, the two copper(I)-containing CPs investigated exhibit the highest efficiency in both reactions, leading selectively to a maximum product yield of 92% (and TON up to 1.5 x 10(3)) in the oxidation of 1-phenylethanol and of 11% in the oxidation of cydohexane, the latter value being higher than that granted by the current industrial process.

Cyclopentadienyl-functionalised N-heterocyclic carbenes: synthesis, coordination to Mo, Ru, Rh

Dissertation presented to obtain the Ph.D degree in Chemistry

Design of the ISePorto robocup Middle-Size League Robotic Soccer Team: Control, Localisation and Coordination

Proceedings of the 10th Mediterranean Conference on Control and Automation - MED2002 Lisbon, Portugal, July 9-12, 2002

Enzymatic activity mastered by altering metal coordination spheres

J Biol Inorg Chem (2008) 13:1185–1195 DOI 10.1007/s00775-008-0414-3

Sarcoplasmic reticulum calcium ATPase is inhibited by organic vanadium coordination compounds: pyridine-2,6-dicarboxylatodioxovanadium(V), BMOV, and an amavadine analogue

Inorg Chem. 2008 Jul 7;47(13):5677-84. doi: 10.1021/ic702405d

Periplasmic nitrate reductase revisited: a sulfur atom completes the sixth coordination of the catalytic molybdenum

J Biol Inorg Chem. 2008 Jun;13(5):737-53. doi: 10.1007/s00775-008-0359-6

Towards an engine for coordination-based architectural reconfigurations

Software reconfigurability became increasingly relevant to the architectural process due to the crescent dependency of modern societies on reliable and adaptable systems. Such systems are supposed to adapt themselves to surrounding environmental changes with minimal service disruption, if any. This paper introduces an engine that statically applies reconfigurations to (formal) models of software architectures. Reconfigurations are specified using a domain specific language— ReCooPLa—which targets the manipulation of software coordinationstructures,typicallyusedinservice-orientedarchitectures(soa).Theengine is responsible for the compilation of ReCooPLa instances and their application to the relevant coordination structures. The resulting configurations are amenable to formal analysis of qualitative and quantitative (probabilistic) properties.

Coordinación socio-política. Redes de influencia y estructuras de poder en CórdobaSocio-political coordination. Influence Networks and power structures in Córdoba.

Los mecanismos de producción y reproducción de la influencia política es una importante área de estudio de la ciencia política en las últimas décadas. En la misma se han disputado diferentes teorías, desde las que plantean la influencia predominante de grupos de poder y sectores corporativos tanto en las decisiones del estado como en las no decisiones, hasta los que plantean que existe la puja de diferentes intereses dentro del Estado pero que no existe ningún grupo predominante. El análisis de redes (network analysis) permite estudiar este objeto mediante la observación de la estructura de relaciones de los actores influyentes dentro de la política provincial. En esta area de estudio, este proyecto propone estudiar de qué manera se produce y reproduce la influencia política en la Provincia de Córdoba.Las hipótesis que plantea el proyecto son las siguientes: H1- La estructura del poder socio-político provincial adquiere una configuración reticular en la que existe un núcleo de actores que representan intereses tradicionales organizados y permite un escaso acceso de nuevas organizaciones que defienden intereses sociales difusos. H2- En el proceso de influencia sociopolítica provincial operan mecanismos de influencia interpersonales directos e indirectos (Brokerage) que permiten a los actores acceder e influir en los decisores públicos. H3- En el proceso de influencia socio-política interviene una diversidad de recursos de poder que los actores utilizan para influir las políticas públicas. Para esto se propone como objetivos del proyecto los siguientes: 1- Identificar y analizar la estructura de poder e influencia que subyace a la política provincial. 2- Analizar los intereses, actores y sectores incluidos y excluidos de la estructura de influencia política. 3- Analizar los mecanismos y recursos de producción y reproducción del poder y la influencia. 4- Analizar las áreas de política del estado provincial que resultan lugar de influencia de los actores y sectores que configuran la estructura de poder socio-política. 5- Analizar el sistema de decisión colectiva (policy domain) en dos áreas de política provincial. 6- Analizar los recursos que posibilitan a los actores ejercer poder e influencia en las áreas de políticas estudiadas. Para la verificación empírica de las hipótesis se realiza un diseño de investigación que incluye el mapeo y análisis de dos tipos de redes políticas diferentes, la "red de influencia en la política provincial" y la red de influencia en un "área de políticas públicas". La reconstrucción de las redes políticas se realizará mediante entrevistas semi-estructuradas a actores sociales y políticos en un muestreo no probabilístico de tipo "bola de nieve". La investigación pretende realizar un aporte a la comprensión de la coordinación política y, en tal sentido, espera alcanzar una adecuada descripción y comprensión de los procesos de influencia y de estructuración del poder en la Provincia de Córdoba.

Coordination chemistry of acrylamide and N-pyrazolylpropanamide : syntheses and structures

Magdeburg, Univ., Fak. für Verfahrens- und Systemtechnik, Diss., 2006

effectiveness of partial coordination among decentralized institutions

Externalities, fiscal competition, partial coordination, wage formation

Observability and overcoming coordination failure in organizations

Many organizations suffer poor performance because its members fail to coordinate on efficient patterns of behavior. In previous research, we have shown that financial incentives can be used to find a way out of such performance traps. Here we examine the sensitivity of this result to the ability of people to observe others' choices. Our experiments are set in a corporate environment where subjects' payoffs depend on coordinating at high effort levels; the underlying game being played repeatedly by the employees of an experimental firm is a weak-link game. Treatments vary along two dimensions. First, subjects either start with low financial incentives for coordination, which typically leads to coordination failure, and then are switched to higher incentives or start with high incentives, which typically yield effective coordination, and are switched to low incentives. Second, as the key treatment variable, subjects either observe the effort levels chosen by all employees in their experimenta

A change would do you good . . . An experimental study on how to overcome coordination failure in organizations

Many organizations suffer poor performance because individuals within the organization fail to coordinate on efficient patterns of behavior. Using controlled laboratory experiments, we study how financial incentives can be used to find a way out of such performance traps. Our experiments are set in a corporate environment where subjects' payoffs depend on coordinating at high effort levels; the underlying game being played repeatedly by employees is a weak-link game. In an initial phase, the benefits of coordination are low relative to the cost of increased effort. Play in this initial phase typically converges to an inefficient outcome with employees failing to coordinate at high effort levels. The experimental design then explores the effects of varying the financial incentives to coordinate at a higher effort level. We find that an increase in the benefits of coordination leads to improved coordination, but, surprisingly, large increases have no more impact than small increases. Once subj