«El ingenioso hidalgo don Quijote» (1605), satire ménippéenne : (Prosas nuevas -V-: cartas, relaciones, «Lazarillos», «Guzmanes» y «Quijotes»)

Convocar marbetes como «novela» o «parodia de libros de caballerías» es tan natural que pocas veces nos fijamos en la tradición narrativa en la cual se situaba El ingenioso hidalgo don Quijote de la Mancha. Este artículo propone recuperar la vena jocoseria y los textos fundamentales de Luciano que hicieron posible la ficción de Cervantes. Sin atar el libro de 1605 al género de la sátira menipea, sí lo define como libro menipeano. La adaptación alemaniana (Primera parte de Guzmán de Alfarache) de la fórmula lucianesca vieja (Historia verdadera, El sueño) y nueva (Segunda parte del Lazarillo, Crotalón) no podía satisfacer a Cervantes : desde esta perspectiva de historia literaria, el Quijote constituye una propuesta narrativa alternativa de prosa menipeana.Utiliser des termes comme « roman » ou « parodie de livres de chevalerie » est tellement naturel que l'on a presque oublié de se demander à quelle tradition narrative se rattache El ingenioso hidalgo don Quijote de la Mancha. Cet article s'emploie à récupérer la veine sério-comique et les textes fondamentaux de Lucien de Samosate qui rendirent possible la fiction de Cervantès. Si ce livre n'est pas une satire ménippée, il n'en demeure pas moins un livre ménippéen. L'adaptation alémanienne (Primera parte de Guzmán de Alfarache) de la formule lucianesque ancienne (Histoire véritable, Le songe) et nouvelle (Segunda parte del Lazarillo, Crotalón) ne pouvait complètement satisfaire Cervantès : dans ce cadre, qui relève de l'histoire littéraire, on verra ainsi que le Quichotte constitue une proposition narrative alternative de prose ménippéenne.Using categories such as "novel" or "parody of tale of chivalry" is such a common thing that we rarely consider the narrative tradition within which El ingenioso hidalgo don Quijote de la Mancha fell. This article comes back to the jocoseria inspiration and those among Lucien's fundamental texts which made it possible for Cervantes's fiction to emerge. Without locking his 1605 text in the Menippean satire genre, Cervantes defines it as a Menippean book. Cervantes could not be satisfied with the adaptation by Mateo Alemán (Primera parte de Guzmán de Alfarache) of the old Lucianesque formula (Historia verdadera, El sueño) nor of the short story (Segunda parte del Lazarillo, Crotalón). Envisaged from such a perspective of literary history, the Quijote becomes an alternative to the narrative proposition of Menippean prose

Synthesis, Characterization, and Crystal Structures of a Series of Osmium−Rhodium Mixed-Metal Carbonyl Clusters: [N(PPh₃)₂][Os₆Rh(μ-H)₂(CO)₂₀], [Os₆Rh(μ-H)₇(μ-CO)(CO)₁₈], [Os₆Rh(μ-H)₉(CO)₁₈], and [Os₃Rh(μ-CO)(CO)₉(μ₄-η²-PhC₂Ph)(μ₂-η¹:η²-PhC₂PhH)]

The reaction between [N(PPh3)2][Os3(μ-H)(CO)11] and [Rh(COD)2][SbF6] (COD = cycloocta-1,5-diene) yields the known cluster [Os3Rh(μ-H)3(CO)10(COD)] (1) and the new complex [N(PPh3)2][Os6Rh(μ-H)2(CO)20] (2). Subsequent reaction of 1 with CO gas in CH2Cl2 produces [Os3Rh(μ-H)3(CO)12] (4). Compound 1 also reacts with 1 equiv of [N(PPh3)2][Os3(μ-H)(CO)11] to give 2. Hydrogenation of 1 results in the hydrogen-rich cluster [Os6Rh(μ-H)9(CO)18] (5) in moderate yield. Reaction of 1 with diphenylacetylene affords [Os3Rh(μ-CO)(CO)9(μ4-η2-PhC2Ph)(μ2-η1:η2-PhC2PhH)] (6). On the other hand, the unsaturated cluster [Os3(μ-H)2(CO)10] reacts with [Rh(dppm)2][BF4] (dppm = bis(diphenylphosphino)methane) to give [Os6Rh(μ-H)7(μ-CO)(CO)18] (3) in good yield. The crystal structures of 2, 3, 5, and 6 were determined. Clusters, 2, 3, and 5 consist of a central rhodium atom linking two triosmium units; however, the rhodium atom of 2 bridges two triosmium units, while 3 and 5 possess a sandwich-type structure. Complex 6 has a butterfly arrangement of three osmium atoms and one rhodium atom which contains a diphenylacetylene fragment in a μ4-η2 arrangement and an alkenyl group in a μ2-η1:η2 configuration

Synthesis, Characterization, and Crystal Structures of a Series of Osmium−Rhodium Mixed-Metal Carbonyl Clusters: [N(PPh₃)₂][Os₆Rh(μ-H)₂(CO)₂₀], [Os₆Rh(μ-H)₇(μ-CO)(CO)₁₈], [Os₆Rh(μ-H)₉(CO)₁₈], and [Os₃Rh(μ-CO)(CO)₉(μ₄-η²-PhC₂Ph)(μ₂-η¹:η²-PhC₂PhH)]

The reaction between [N(PPh3)2][Os3(μ-H)(CO)11] and [Rh(COD)2][SbF6] (COD = cycloocta-1,5-diene) yields the known cluster [Os3Rh(μ-H)3(CO)10(COD)] (1) and the new complex [N(PPh3)2][Os6Rh(μ-H)2(CO)20] (2). Subsequent reaction of 1 with CO gas in CH2Cl2 produces [Os3Rh(μ-H)3(CO)12] (4). Compound 1 also reacts with 1 equiv of [N(PPh3)2][Os3(μ-H)(CO)11] to give 2. Hydrogenation of 1 results in the hydrogen-rich cluster [Os6Rh(μ-H)9(CO)18] (5) in moderate yield. Reaction of 1 with diphenylacetylene affords [Os3Rh(μ-CO)(CO)9(μ4-η2-PhC2Ph)(μ2-η1:η2-PhC2PhH)] (6). On the other hand, the unsaturated cluster [Os3(μ-H)2(CO)10] reacts with [Rh(dppm)2][BF4] (dppm = bis(diphenylphosphino)methane) to give [Os6Rh(μ-H)7(μ-CO)(CO)18] (3) in good yield. The crystal structures of 2, 3, 5, and 6 were determined. Clusters, 2, 3, and 5 consist of a central rhodium atom linking two triosmium units; however, the rhodium atom of 2 bridges two triosmium units, while 3 and 5 possess a sandwich-type structure. Complex 6 has a butterfly arrangement of three osmium atoms and one rhodium atom which contains a diphenylacetylene fragment in a μ4-η2 arrangement and an alkenyl group in a μ2-η1:η2 configuration

Synthesis, Characterization, and Crystal Structures of a Series of Osmium−Rhodium Mixed-Metal Carbonyl Clusters: [N(PPh₃)₂][Os₆Rh(μ-H)₂(CO)₂₀], [Os₆Rh(μ-H)₇(μ-CO)(CO)₁₈], [Os₆Rh(μ-H)₉(CO)₁₈], and [Os₃Rh(μ-CO)(CO)₉(μ₄-η²-PhC₂Ph)(μ₂-η¹:η²-PhC₂PhH)]

The reaction between [N(PPh3)2][Os3(μ-H)(CO)11] and [Rh(COD)2][SbF6] (COD = cycloocta-1,5-diene) yields the known cluster [Os3Rh(μ-H)3(CO)10(COD)] (1) and the new complex [N(PPh3)2][Os6Rh(μ-H)2(CO)20] (2). Subsequent reaction of 1 with CO gas in CH2Cl2 produces [Os3Rh(μ-H)3(CO)12] (4). Compound 1 also reacts with 1 equiv of [N(PPh3)2][Os3(μ-H)(CO)11] to give 2. Hydrogenation of 1 results in the hydrogen-rich cluster [Os6Rh(μ-H)9(CO)18] (5) in moderate yield. Reaction of 1 with diphenylacetylene affords [Os3Rh(μ-CO)(CO)9(μ4-η2-PhC2Ph)(μ2-η1:η2-PhC2PhH)] (6). On the other hand, the unsaturated cluster [Os3(μ-H)2(CO)10] reacts with [Rh(dppm)2][BF4] (dppm = bis(diphenylphosphino)methane) to give [Os6Rh(μ-H)7(μ-CO)(CO)18] (3) in good yield. The crystal structures of 2, 3, 5, and 6 were determined. Clusters, 2, 3, and 5 consist of a central rhodium atom linking two triosmium units; however, the rhodium atom of 2 bridges two triosmium units, while 3 and 5 possess a sandwich-type structure. Complex 6 has a butterfly arrangement of three osmium atoms and one rhodium atom which contains a diphenylacetylene fragment in a μ4-η2 arrangement and an alkenyl group in a μ2-η1:η2 configuration

A Simple, Regioselective Synthesis of 1,4-Bis(<i>tert</i>-butoxycarbonylmethyl)- tetraazacyclododecane

A convenient synthetic route to 1,4-bis(tert-butoxycarbonylmethyl)tetraazacyclododecane (cyclen) (1) with high yield and excellent regioselectivity is described. Compound 1 reacted with a range of functionalized alkyl halides under two reaction conditions to give mono-N-alkylated 1,4-bis(tert-butoxycarbonylmethyl)tetraazacyclododecane (2−9) in good yield

Osmium(VI) Nitrido and Osmium(IV) Phosphoraniminato Complexes Containing Schiff Base Ligands

A series of osmium(VI) nitrido complexes containing Schiff base ligands, [OsVI(N)(L)Cl] (L = salophen or salen), have been synthesized by reaction of the ligand with [NBun4][OsVI(N)Cl4] in the presence of 2,6-dimethylpyridine. The ν(Os⋮N) for the salophen complexes occur at around 1070 cm-1 and are insensitive to the nature of the substituents present on the Schiff base ligand. The structures of [Os(N)(salophen)(MeOH)]ClO4 and [Os(N)(5,5-Cl2salophen)(MeOH)]ClO4 have been determined by X-ray crystallography, and the Os⋮N bond distances are 1.651 and 1.66 Å, respectively. The osmium(VI) nitrido complexes react rapidly with triphenylphosphine to produce the corresponding osmium(IV) phosphoraniminato complexes, [OsIV(NPPh3)(L)Cl]. The osmium(IV) complexes exhibit reversible OsV/IV and OsIV/III couples in cyclic voltammetry. The E1/2 values show linear correlations with the Hammett constants σp of the substituents on the Schiff base ligand. The structure of [OsIV(NPPh3)(salophen)Cl] has been determined by X-ray crystallography. The rather long Os−N(P) bond length (1.92 Å) and acute Os−N−P bond angle (149.6°) suggest that there is no significant multiple-bond character in the Os−N bond. The kinetics of nitrogen atom transfer from a series of 5,5‘-disubstituted salophen nitrido complexes to PPh3 have been studied in CH3CN at 25.0 °C by stopped-flow spectrophotometric method. The following rate law was obtained:  −d[Os(VI)]/dt = k2[Os(VI)][PPh3]. The reactivities of the complexes were found to follow a Hammett correlation of log(kX/kH) with σp, with a ρ value of 1.9 ± 0.1. The positive ρ value is consistent with a transition state involving electrophilic attack by the nitrido ligand on the phosphorus atom

Heterometallic Osmium−Mercury Chain Structures Linking Two {Os₃(CO)₁₀(μ-X)} Subunits (X = Cl, Br, I): Syntheses and Molecular Structures of [{Os₃(CO)₁₀(μ-X)}₂(μ₄-Hg)] (X = Cl, I), [{Os₃(CO)₁₀(μ-Cl)}₂{μ-HgOs(CO)₄}₂], and <i>cis</i>-[Os(CO)₄{(μ-Hg)Os₃(CO)₁₀(μ-Cl)}₂]

Treatment of RHgCl (R = Me, Et, Ph, Fc) with the activated cluster [Os3(CO)10(NCMe)2] produces the osmium−mercury mixed-metal clusters [{Os3(CO)10(μ-Cl)}2(μ4-Hg)] (1a) and [{Os3(CO)10(μ-Cl)}2{μ-HgOs(CO)4}2] (2a) in low yields. Cluster 1a bears a central wingtip mercury atom simultaneously bridging two {Os3(CO)10(μ-Cl)} units. Cluster 2a comprises an unprecedented decanuclear osmium−mercury framework in which there is a central linear “Hg−{Os(CO)4}2−Hg” molecular backbone with the two Os(CO)4 fragments arranged in a staggered conformation. Cluster 2a is thermally unstable and converts slowly to cis-[Os(CO)4{(μ-Hg)Os3(CO)10(μ-Cl)}2] (4a) via the extrusion of an Os(CO)4 moiety under ambient conditions. Cluster 4a comprises two {(μ-Hg)Os3(CO)10(μ-Cl)} subcluster units bonded to a central Os(CO)4 moiety in a cis configuration. Similar reactions with PhHgBr and MeHgI have also been investigated. Cluster 1a crystallizes in the triclinic space group P1̄ with a = 9.112(2) Å, b = 12.314(2) Å, c = 15.501(4) Å, α = 84.92(2),° β = 88.26(3),° γ = 79.52(2)° and Z = 2. Cluster 2a crystallizes in the triclinic space group P1̄ with a = 13.306(2) Å, b = 20.768(5) Å, c = 9.771(4) Å, α = 96.36(3),° β = 90.50(2),° γ = 98.81(2)° and Z = 2. Cluster 4a crystallizes in the triclinic space group P1̄ with a = 18.356(2) Å, b = 19.100(3) Å, c = 14.478(2) Å, α = 89.783(2),° β = 113.19(2),° γ = 113.70(2)° and Z = 4

Osmium(VI) Nitrido and Osmium(IV) Phosphoraniminato Complexes Containing Schiff Base Ligands

A series of osmium(VI) nitrido complexes containing Schiff base ligands, [OsVI(N)(L)Cl] (L = salophen or salen), have been synthesized by reaction of the ligand with [NBun4][OsVI(N)Cl4] in the presence of 2,6-dimethylpyridine. The ν(Os⋮N) for the salophen complexes occur at around 1070 cm-1 and are insensitive to the nature of the substituents present on the Schiff base ligand. The structures of [Os(N)(salophen)(MeOH)]ClO4 and [Os(N)(5,5-Cl2salophen)(MeOH)]ClO4 have been determined by X-ray crystallography, and the Os⋮N bond distances are 1.651 and 1.66 Å, respectively. The osmium(VI) nitrido complexes react rapidly with triphenylphosphine to produce the corresponding osmium(IV) phosphoraniminato complexes, [OsIV(NPPh3)(L)Cl]. The osmium(IV) complexes exhibit reversible OsV/IV and OsIV/III couples in cyclic voltammetry. The E1/2 values show linear correlations with the Hammett constants σp of the substituents on the Schiff base ligand. The structure of [OsIV(NPPh3)(salophen)Cl] has been determined by X-ray crystallography. The rather long Os−N(P) bond length (1.92 Å) and acute Os−N−P bond angle (149.6°) suggest that there is no significant multiple-bond character in the Os−N bond. The kinetics of nitrogen atom transfer from a series of 5,5‘-disubstituted salophen nitrido complexes to PPh3 have been studied in CH3CN at 25.0 °C by stopped-flow spectrophotometric method. The following rate law was obtained:  −d[Os(VI)]/dt = k2[Os(VI)][PPh3]. The reactivities of the complexes were found to follow a Hammett correlation of log(kX/kH) with σp, with a ρ value of 1.9 ± 0.1. The positive ρ value is consistent with a transition state involving electrophilic attack by the nitrido ligand on the phosphorus atom

Photochromic Thienylpyridine–Bis(alkynyl)borane Complexes: Toward Readily Tunable Fluorescence Dyes and Photoswitchable Materials

A series of diarylethene-containing N^∧C chelated thienylpyridine–bis(alkynyl)borane complexes has been designed and synthesized. Their photophysical and photochromic properties have been investigated and presented. The characteristic low-energy absorption band of their closed forms could be readily tuned from the visible range to the near-infrared region

Photochromic Thienylpyridine–Bis(alkynyl)borane Complexes: Toward Readily Tunable Fluorescence Dyes and Photoswitchable Materials

A series of diarylethene-containing N^∧C chelated thienylpyridine–bis(alkynyl)borane complexes has been designed and synthesized. Their photophysical and photochromic properties have been investigated and presented. The characteristic low-energy absorption band of their closed forms could be readily tuned from the visible range to the near-infrared region