Electrocarboxylation of chloroacetonitrile mediated by electrogenerated cobalt(I) phenanthroline

The electrocarboxylation of chloroacetonitrilemediated by [Co(II)(phen)3]2+ has been investigated. Cyclic voltammetry studies of [Co(II)(phen)3]2+ have shown that [Co(I)(phen)3]+, an 18 electron complex, activates chloroacetonitrile by an oxidative addition through the loss of a phenanthroline ligand to give [RCo(III)(phen)2Cl]+. The unstable one-electron-reduced complex underwent Co–C bond cleavage. In carbon dioxide saturated solution, CO2 insertion proceeds after reduction of the alkylcobalt complex. A catalytic current is observed which corresponds to the electrocarboxylation of chloroacetonitrile into cyanoacetic acid. Electrolyses confirmed the process and gave faradic yield of 62% in cyanoacetic acid at potentials that are about 0.3 V less cathodic than the one required for Ni(salen)

Electrocarboxylation of chloroacetonitrile by a Cobalt(I) complex of terpyridine

The electrocarboxylation of chloroacetonitrile (NC–CH2–ClRCl) mediated by [CoIIL2]2+ (L = terpyridine) was investigated by cyclic voltammetry. Electrochemical studies under argon atmosphere showed that the monoelectronic reduction of [CoIIL2]2+ yielded a Cobalt(I) complex which after the loss of a terpyridine ligand reacted with chloroacetonitrile. The oxidative addition of chloroacetonitrile on [CoIL]+ gave an alkylCobalt(III) complex [R–CoIIIL]2+ which was reduced into an alkylCobalt(II) complex, highly unstable and decomposed into an alkyl anion and a Cobalt(II) complex. Under carbon dioxide atmosphere, Cobalt(I) complex was shown to be unreactive towards CO2 but CO2 insertion was observed in the alkylCobalt(III) complex [R–CoIIIL] 2+ giving probably a CO2 adduct [R–CoIIIL(CO2)]2+. This adduct presented a strong adsorption at the carbon electrode and was reduced at potential less cathodic than the one of alkylCobalt(III) complex. After reduction, the carboxylate RCO2− (NC–CH2–CO2−) was released and a catalytic bielectronic carboxylation of chloroacetonitrile took place. Controlled potential electrolyses confirmed the catalytic process and gave for cyanoacetic acid faradic yields up to 60% under low overpotential conditions

Observable and unobservable variables in the theory of the equilibrium rate of unemployment, a comparison between France and the United States

This paper confronts, theoretically and empirically, two estimation methods for the Equilibrium Rate of Unemployment (ERU). By introducing observable variables into the TV-NAIRU approach and unobservable variables into the structural approach, we show how these two methods can converge even though their diagnoses differ appreciably in the French case. We considerably improve the econometric and explanatory properties of the French TV-NAIRU model by identifying some of its determinants (interest rates, labour productivity). Moreover, by distinguishing between the concepts of long-term and medium-term ERU, we separate the medium- from the long-term and the observable from the unobservable components of the ERU.

Presentation of the Three-ME model: Multi-sector Macroeconomic Model for the Evaluation of Environmental and Energy policy

This paper presents the structure and the main properties of Three-ME. This new model of the French economy has been especially designed to evaluate the medium and long term impact of environmental and energy policies at the macroeconomic and sector levels. To do so Three-ME combines two important features. Firstly, it has the main characteristics of neo-Keynesian models by assuming a slow adjustment of effective quantities and prices to their notional level. Compared to standard multi-sectors CGEM, this has the advantage to allow for the existence of under-optimum equilibriums such as the presence of involuntary unemployment. Secondly, production and consumption structures are represented with a generalized CES function which allows for the elasticity of substitution to differ between each couple of inputs or goods. This is an improvement compared to the standard approach that uses nested CES functions which has the disadvantage to impose a common elasticity of substitution between the goods located in two different nested structures.neo-Keynesian model, macroeconomic modeling, energy and environmental policy modeling

J. Gerald Kennedy, Strange Nation: Literary Nationalism and Cultural Conflict in the Age of Poe

Compte-rendu : New York: Oxford University Press, 2016, 472 pages.International audienc

Kant : "l'única prova possible per a una demostració de l'existència de Déu"

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Lo natural y lo artificial en Aristóteles y Francis Bacon : bases para la tecnología moderna

El poder de la tecnología contemporánea depende de su capacidad para imponerse a lo que la naturaleza ya tiene dado. En términos de la ontología griega clásica, dicha capacidad se puede formular diciendo que la tecnología puede sustituir lo natural por lo artificial. Para entender el significado de esta sustitución, el presente artículo estudia la concepción de lo natural y lo artificial en Aristóteles y en Francis Bacon, y analiza sus diferencias. Con ello se descubren los cambios que el mundo moderno realiza con respecto a la filosofía de la antigüedad, cambios que justifican la creencia contemporánea en el poder de la técnica y que sientan las bases de la tecnología moderna.The power of contemporary technology depends on its ability to override what nature has already given. In terms of classical Greek ontology, such capacity can be formulated saying that technology can replace natural by artificial. To understand the meaning of this substitution, this article examines conception of the natural and the artificial in Aristotle and Francis Bacon, and analyzes their differences. This will discover the changes that the modern world make about the philosophy of antiquity, changes that justify the belief in the power of contemporary technics, and which lay the foundations of modern technology

Una crònica de Heidegger i «l'escàndol de la filosofia del segle xx»

Amb la publicació, el 1927, d'Ésser i temps, Heidegger es guanya una reputació internacional. Però el 1933, Heidegger, el filòsof mundialment reconegut, esdevé Heidegger el nazi. La simpatia de Heidegger pels nazis ha estat qualificada de «l'escàndol de la filosofia del segle XX». La història oficial de la implicació de Heidegger -que és la recolzada pel mateix Heidegger i pels seus apologistes- la veu com una implicació política de curta durada. D'altra banda, alguns crítics desqualifiquen el treball filosòfic de Heidegger a causa de la seva lleialtat al nazisme, i així mostren la relació intrínseca entre la filosofia de Heidegger i la seva política. Aquest article, en canvi, proposa una tercera via d'aproximació al tema, molt més fructífera. En aquesta línia, es troben Foucault i Agamben. Es tracta d'assumir que Heidegger, pel fet d'haver comprès el nazisme, està en millors condicions que qualsevol altre filòsof per facilitar-nos-en la superació. Segons això, Heidegger serà un testimoni de l'encara avui dia imperant biopolítica.With the publication in 1927 of Being and Time Heidegger assured his international reputation. But in 1933 Heidegger the world-renowned philosopher became Heidegger the Nazi. The Heidegger's sympathy for the Nazis has been named «the scandal of philosophy of century 20th». The official story of Heidegger's involvement -that is, the one endorsed by Heidegger himself and his apologists- goes something like short-lived political involvement. On the other hand, critics disqualify the philosophical work of Heidegger because of their allegiance to Nazism, and, this way, they show the intrinsic relationship between Heidegger's philosophy and his politics. This article, however, proposes one third via of approach to the subject, much more fruitful. In this line Foucault and Agamben are. It is to assume that Heidegger, for the fact of having understood the Nazism, is under better conditions that any other philosopher to facilitate us its overcoming. According to this Heidegger will be a testimony of biopolitics, still prevailing nowadays

Heidegger y la cuestión de la técnica

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