Oxidoperoxidomolybdenum(VI) complexes with acylpyrazolonate ligands: synthesis, structure and catalytic properties

Oxidoperoxido–molybdenum(VI) complexes containing acylpyrazolonate ligands were obtained by reaction of [Mo(O)(O)2(H2O)n] with the corresponding acylpyrazolone compounds HQR. Complexes Ph4P[Mo(O)(O2)2(QR)] (R = neopentyl, 1; perfluoroethyl, 2; hexyl, 3; phenyl, 4; naphthyl, 5; methyl, 6; cyclohexyl, 7; ethylcyclopentyl, 8) were obtained if the reaction was carried out with one equivalent of HQR in the presence of Ph4PCl. Alternatively, neutral complexes [Mo(O)(O2)(QR)2] (R = neopentyl, 9; hexyl, 10; cyclohexyl, 11) were formed when two equivalents of HQR were used in the reaction. These complexes were isolated in good yields as yellow or yellow-orange crystalline solids and were spectroscopically (IR, 1H, 13C{1H} and 31P{1H} NMR), theoretically (DFT) and structurally characterised (X-ray for 1, 2, 9 and 10). Compounds 1 and 9 were selected to investigate their catalytic behaviour in epoxidation of selected alkenes and oxidation of selected sulphides, while 10 and 11 were tested as catalyst precursors in the deoxygenation of selected epoxide substrates to alkenes, using PPh3 as the oxygen-acceptor. Complexes Ph4P[Mo(O)(O2)2(QR)] were shown to be poor catalyst precursors in oxidation reactions, while the activity of [Mo(O)(O2)(QR)2] species is good in all the studied reactions and comparable to related oxidoperoxido–molybdenum(VI) complexes. Complex [Mo(O)2(QC6)2], 12, was obtained by treatment of 10 with one equivalent of PPh3, demonstrating that the first step in the epoxide deoxygenation mechanism was the oxygen atom transfer toward the phosphane.Junta de Andalucía (Proyecto de Excelencia, FQM-7079)Universidad de Sevilla (VI Plan Propio

El Barroco: una mirada a través del arte. Propuesta de mejora para una situación de aprendizaje

En el presente trabajo contemplamos el diseño, desarrollo, análisis crítico y propuesta de mejora de una situación de aprendizaje, teniendo en cuenta la legislación vigente y partiendo de presupuestos innovadores propios de la investigación educativa actual en lo que respecta a la selección y organización de contenidos, la metodología aplicada y los criterios de evaluación. La problemática que centra esta propuesta didáctica es el Arte Barroco, un asunto que consideramos potencialmente atractivo por su interés para la disciplina, su posible vinculación con problemas actuales y las posibilidades que ofrece para enriquecer el conocimiento cotidiano de los alumnos y trabajar contenidos metadisciplinares. Tras una primera parte en la que se presenta el diseño inicial, procedemos a evaluar los resultados derivados de su experimentación durante las prácticas, para culminar en la consecuente propuesta de mejoraMAES. Máster Universitario en Profesorado de Enseñanza Secundaria Obligatoria y Bachillerato, Formación Profesional y Enseñanza de Idioma

Oxidoperoxidomolybdenum(VI) complexes with acylpyrazolonate ligands: synthesis, structure and catalytic properties

Oxidoperoxido-molybdenum(vi) complexes containing acylpyrazolonate ligands were obtained by reaction of [Mo(O)(O)(HO)] with the corresponding acylpyrazolone compounds HQ. Complexes PhP[Mo(O)(O)(Q)] (R = neopentyl, 1; perfluoroethyl, 2; hexyl, 3; phenyl, 4; naphthyl, 5; methyl, 6; cyclohexyl, 7; ethylcyclopentyl, 8) were obtained if the reaction was carried out with one equivalent of HQ in the presence of PhPCl. Alternatively, neutral complexes [Mo(O)(O)(Q)] (R = neopentyl, 9; hexyl, 10; cyclohexyl, 11) were formed when two equivalents of HQ were used in the reaction. These complexes were isolated in good yields as yellow or yellow-orange crystalline solids and were spectroscopically (IR, H, C{H} and P{H} NMR), theoretically (DFT) and structurally characterised (X-ray for 1, 2, 9 and 10). Compounds 1 and 9 were selected to investigate their catalytic behaviour in epoxidation of selected alkenes and oxidation of selected sulphides, while 10 and 11 were tested as catalyst precursors in the deoxygenation of selected epoxide substrates to alkenes, using PPh as the oxygen-acceptor. Complexes PhP[Mo(O)(O)(Q)] were shown to be poor catalyst precursors in oxidation reactions, while the activity of [Mo(O)(O)(Q)] species is good in all the studied reactions and comparable to related oxidoperoxido-molybdenum(vi) complexes. Complex [Mo(O)(Q)], 12, was obtained by treatment of 10 with one equivalent of PPh, demonstrating that the first step in the epoxide deoxygenation mechanism was the oxygen atom transfer toward the phosphane.This research was supported by the Junta de Andalucía (Proyecto de Excelencia, FQM-7079) and by the Universities of Sevilla (VI Plan Propio) and Camerino