Nuevos datos acerca de los repertorios teatrales en el primer catálogo de «El peregrino en su patria»

En este artículo se muestra cómo los títulos que contienen los repertorios de los autores de comedias presentes en El peregrino en su patria de 1604 están dispuestos según un orden cronológico, aunque con algunos matices y no pocas excepciones. Además, se amplían los repertorios descubiertos por Thornton Wilder y se afina la fecha de composición de varias obras, prestando especial atención a textos que se han perdido, como La perdición de España, La gobernadora, La gran pintora, La bella gitana o La toma de Álora. Finalmente, el presente artículo pretende mostrar de un modo práctico cómo una base de datos digital como el Diccionario biográfico de actores del teatro clásico español (DICAT) puede resultar de gran ayuda a la hora de resolver algunos de los problemas clásicos de la filología en general y del teatro del Siglo de Oro en particular.This paper shows that the plays contained in the repertoire of the autores de comedias which appear in El peregrino en su patria (1604) are organised chronologically, although there are some nuances and exceptions. The article also expands the repertoire discovered by Thornton Wilder and sets the date of composition for some plays, paying special attention to lost texts such as La perdición de España, La gobernadora, La gran pintora, La bella gitana or La toma de Álora. Finally, this paper attempts to show in a practical way that a database such as the Diccionario biográfico de actores del teatro clásico español (DICAT) can be extremely helpful when it comes to dealing with some of the philology's classical problems in general and those of the theatre of the Golden Age in particular

Synthesis and Reactivity of the Methylene Arenium Form of a Benzyl Cation, Stabilized by Complexation

Benzyl cations are unstable intermediates involved in various chemical and biological processes. Two extreme resonance forms of these cations include positive charge localization at the methylene carbon or delocalization in the ring, the latter, nonaromatic form, termed “methylene arenium”. The preparation of the discrete methylene arenium compound, stabilized by coordination to a metal (palladium) center, is described. It was fully characterized, including by X-ray diffraction. Reactivity patterns, resulting from charge distribution in the ring, were observed. Upon controlled release of the methylene arenium compound into solution, it demonstrates aromatic benzyl cation reactivity

Electron Transfer−Oxygen Transfer Oxygenation of Sulfides Catalyzed by the H₅PV₂Mo₁₀O₄₀ Polyoxometalate

The oxygenation of sulfides to the corresponding sulfoxides catalyzed by H5PV2Mo10O40 and other acidic vanadomolybdates has been shown to proceed by a low-temperature electron transfer−oxygen transfer (ET−OT) mechanism. First, a sulfide reacts with H5PV2Mo10O40 to yield a cation radical−reduced polyoxometalate ion pair, R2+•,H5PVIVVVMo10O40, that was identified by UV−vis spectroscopy (absorptions at 650 and 887 nm for PhSMe+• and H5PVIVVVMo10O40) and EPR spectroscopy (quintet at g = 2.0079, A = 1.34 G for the thianthrene cation radical and the typical eight-line spectrum for VIV). Next, a precipitate is formed that shows by IR the incipient formation of the sulfoxide and by EPR a VO2+ moiety supported on the polyoxometalate. Dissolution of this precipitate releases the sulfoxide product. ET−OT oxidation of diethylsulfide yielded crystals containing [V(O)(OSEt2)x(solv)5−x]2+ cations and polyoxometalate anions. Under aerobic conditions, catalytic cycles can be realized with formation of mostly sulfoxide (90%) but also some disulfide (10%) via carbon−sulfide bond cleavage

Processes Involved in the Reduction of a Cyclometalated Palladium(II) Complex

Reaction of [Pd(TFA)2] (1; TFA = trifluoroacetate) with 2 equiv of benzyldiisopropylphosphine resulted in formation of the metalated complex [Pd{C6H4(CH2PiPr2)}{(C6H5CH2)PiPr2}(TFA)] (2). The dinuclear trifluoroacetate complex [Pd{C6H4(CH2PiPr2)}(TFA)]2 (3) was formed when the reaction was performed with an equimolar amount of the phosphine. Both complexes were structurally characterized. Reduction of the cyclometalated palladium complex 2 with sodium metal in THF gave a mixture of cis and trans isomers of the dimetalated bis(o-benzyldiisopropylphosphine)palladium(II) (6a,b) and bis(benzyldiisopropylphosphine)palladium(0) (7). A mechanism for the reduction process is presented. Treatment of the reaction mixture of 6a,b and 7 with an equimolar amount of hydrochloric acid led to a mixture of 7, [Pd{C6H4(CH2PiPr2)}{(C6H5CH2)PiPr2}(Cl)] (9), [Pd{(C6H5CH2)PiPr2}2(H)(Cl)] (8), [Pd{(C6H5CH2)PiPr2}2(Cl)2] (4), and both isomeric forms of [Pd{C6H4(CH2PiPr2)}2] (6a,b). All complexes were independently prepared and fully characterized. The addition of another 1 equiv of hydrochloric acid to this reaction mixture resulted in the exclusive formation of 4. Reduction of 4 with sodium metal in THF cleanly yielded the Pd0 complex 7 in high yields, offering a new, facile, and high-yield route toward the synthesis of dicoordinated bis(phosphine) Pd0 complexes. Reaction of 7 with an equimolar amount of HCl led to the clean formation of [Pd{(C6H5CH2)PiPr2}2(H)(Cl)] (8). The addition of another 1 equiv of HCl led to the quantitative formation of 2 and H2. Reactions of 9 and an equimolar amount of NaBHEt3 cleanly yielded complex 7, which was also exclusively formed by treatment of 4 with 2 equiv of NaBHEt3. Mixtures of the cis and trans isomers 6a,b were formed by the addition of 2 equiv of (o-lithiobenzyl)diisopropylphosphine to benzene solutions of bis(diethyl sulfide)palladium dichloride (5) at room temperature

Synthesis and Reactivity of the Methylene Arenium Form of a Benzyl Cation, Stabilized by Complexation

Benzyl cations are unstable intermediates involved in various chemical and biological processes. Two extreme resonance forms of these cations include positive charge localization at the methylene carbon or delocalization in the ring, the latter, nonaromatic form, termed “methylene arenium”. The preparation of the discrete methylene arenium compound, stabilized by coordination to a metal (palladium) center, is described. It was fully characterized, including by X-ray diffraction. Reactivity patterns, resulting from charge distribution in the ring, were observed. Upon controlled release of the methylene arenium compound into solution, it demonstrates aromatic benzyl cation reactivity

In Situ Growth of High Quality Crystals for Organic Electronics

We envisaged that rapid thermal processing (RTP) widely used in semiconductor device fabrication can be employed for fabricating organic crystalline devices since heating and mass transfer are localized within a small area in RTP. This may result in crystal growth at the location relevant to organic device fabrication in situ, for which RTP has not been used so far. We utilized the RTP technique for the growth of high quality organic crystals from thin films of copper phthalocyanine (CuPc) and rubrene. The crystals were grown in situ on silicon surfaces, which were directly used for device fabrication (organic field effect transistors, OFETs, and organic phototransistors, OPTs). For CuPc devices, the mobility was 0.12 ± 0.11 cm2 V–1 s–1, on/off ratio of up to 106, and photo/dark current ratio of P > 105 (for OPT devices). The mobility of rubrene-based OFETs was 0.31 ± 0.15 cm2 V–1 s–1, on/off ratio of up to 105, and photo/dark current ratio of P ≈ 105. The mobilities are similar to those of previously reported single-crystalline CuPc and rubrene OFETs fabricated on untreated surfaces, and the photoresponses are stronger than those of the reported CuPc and rubrene OPTs. RTP is a general and efficient method to grow high quality organic crystals in situ, significantly advancing fabrication methodology for organic electronic and optoelectronic devices

Synthesis and Reactivity of the Methylene Arenium Form of a Benzyl Cation, Stabilized by Complexation

Benzyl cations are unstable intermediates involved in various chemical and biological processes. Two extreme resonance forms of these cations include positive charge localization at the methylene carbon or delocalization in the ring, the latter, nonaromatic form, termed “methylene arenium”. The preparation of the discrete methylene arenium compound, stabilized by coordination to a metal (palladium) center, is described. It was fully characterized, including by X-ray diffraction. Reactivity patterns, resulting from charge distribution in the ring, were observed. Upon controlled release of the methylene arenium compound into solution, it demonstrates aromatic benzyl cation reactivity

Electron Transfer−Oxygen Transfer Oxygenation of Sulfides Catalyzed by the H₅PV₂Mo₁₀O₄₀ Polyoxometalate

The oxygenation of sulfides to the corresponding sulfoxides catalyzed by H5PV2Mo10O40 and other acidic vanadomolybdates has been shown to proceed by a low-temperature electron transfer−oxygen transfer (ET−OT) mechanism. First, a sulfide reacts with H5PV2Mo10O40 to yield a cation radical−reduced polyoxometalate ion pair, R2+•,H5PVIVVVMo10O40, that was identified by UV−vis spectroscopy (absorptions at 650 and 887 nm for PhSMe+• and H5PVIVVVMo10O40) and EPR spectroscopy (quintet at g = 2.0079, A = 1.34 G for the thianthrene cation radical and the typical eight-line spectrum for VIV). Next, a precipitate is formed that shows by IR the incipient formation of the sulfoxide and by EPR a VO2+ moiety supported on the polyoxometalate. Dissolution of this precipitate releases the sulfoxide product. ET−OT oxidation of diethylsulfide yielded crystals containing [V(O)(OSEt2)x(solv)5−x]2+ cations and polyoxometalate anions. Under aerobic conditions, catalytic cycles can be realized with formation of mostly sulfoxide (90%) but also some disulfide (10%) via carbon−sulfide bond cleavage

Processes Involved in the Reduction of a Cyclometalated Palladium(II) Complex

Reaction of [Pd(TFA)2] (1; TFA = trifluoroacetate) with 2 equiv of benzyldiisopropylphosphine resulted in formation of the metalated complex [Pd{C6H4(CH2PiPr2)}{(C6H5CH2)PiPr2}(TFA)] (2). The dinuclear trifluoroacetate complex [Pd{C6H4(CH2PiPr2)}(TFA)]2 (3) was formed when the reaction was performed with an equimolar amount of the phosphine. Both complexes were structurally characterized. Reduction of the cyclometalated palladium complex 2 with sodium metal in THF gave a mixture of cis and trans isomers of the dimetalated bis(o-benzyldiisopropylphosphine)palladium(II) (6a,b) and bis(benzyldiisopropylphosphine)palladium(0) (7). A mechanism for the reduction process is presented. Treatment of the reaction mixture of 6a,b and 7 with an equimolar amount of hydrochloric acid led to a mixture of 7, [Pd{C6H4(CH2PiPr2)}{(C6H5CH2)PiPr2}(Cl)] (9), [Pd{(C6H5CH2)PiPr2}2(H)(Cl)] (8), [Pd{(C6H5CH2)PiPr2}2(Cl)2] (4), and both isomeric forms of [Pd{C6H4(CH2PiPr2)}2] (6a,b). All complexes were independently prepared and fully characterized. The addition of another 1 equiv of hydrochloric acid to this reaction mixture resulted in the exclusive formation of 4. Reduction of 4 with sodium metal in THF cleanly yielded the Pd0 complex 7 in high yields, offering a new, facile, and high-yield route toward the synthesis of dicoordinated bis(phosphine) Pd0 complexes. Reaction of 7 with an equimolar amount of HCl led to the clean formation of [Pd{(C6H5CH2)PiPr2}2(H)(Cl)] (8). The addition of another 1 equiv of HCl led to the quantitative formation of 2 and H2. Reactions of 9 and an equimolar amount of NaBHEt3 cleanly yielded complex 7, which was also exclusively formed by treatment of 4 with 2 equiv of NaBHEt3. Mixtures of the cis and trans isomers 6a,b were formed by the addition of 2 equiv of (o-lithiobenzyl)diisopropylphosphine to benzene solutions of bis(diethyl sulfide)palladium dichloride (5) at room temperature

Facile Conversion of Alcohols into Esters and Dihydrogen Catalyzed by New Ruthenium Complexes [<i>J. Am. Chem. Soc.</i> <b>2005</b>, <i>127</i>, 10840−10841].

Facile Conversion of Alcohols into Esters and Dihydrogen Catalyzed by New Ruthenium Complexes [J. Am. Chem. Soc. 2005, 127, 10840−10841]