La importancia de la personalidad del traductor en los itinerarios de especialidad y en la selección de personal

Treball Final de Grau en Traducció i Interpretació. Codi: TI0983. Curs acadèmic: 2016/2017A pesar de que a simple vista no lo pueda parecer, la personalidad de los traductores influye mucho más de lo que se cree en el proceso traductor y en la toma de decisiones, como han puesto de manifiesto estudios empíricos. Para analizar cuáles son las diferencias individuales en la personalidad de los traductores en la elección del itinerario de especialidad, se ha llevado a cabo un estudio con los estudiantes de los cuatro itinerarios de traducción de la Universidad Jaume I, a fin de ver si podemos identificar los rasgos típicos de los estudiantes de cada itinerario. Además, dada la gran importancia de la personalidad en las tareas de traducción, también se ha entrevistado a responsables de tres agencias de traducción para ver si la personalidad de los traductores es un factor relevante a la hora de reclutar personal. Se ha comprobado así que sí hay algunos rasgos comunes en la personalidad de los estudiantes de cada itinerario y que realmente esta cuestión no es un factor relevante en las agencias de traducción, sino que se valora, sobre todo, el trabajo diario y la calidad de las pruebas de traducción

Tuning of the Properties of Transition-Metal Bispidine Complexes by Variation of the Basicity of the Aromatic Donor Groups

Bispidines (3,7-diazabicyclo[3.3.1]­nonanes) as very rigid and highly preorganized ligands find broad application in the field of coordination chemistry, and the redox potentials of their transition-metal complexes are of importance in oxidation reactions by high-valent iron complexes, aziridination catalyzed by copper complexes, and imaging by ⁶⁴Cu positron emission tomography tracers. Here, we show that the redox potentials and stability constants of the copper­(II) complexes of 15 tetradentate bispidines can be varied by substitution of the pyridine rings (variation of the redox potential over ca. 450 mV and of the complex stability over approximately 10 log units). It is also shown that these variations are predictable by the p<i>K</i>_a values of the pyridine groups as well as by the Hammett parameters of the substituents, and the density functional theory based energy decomposition analysis also allows one to accurately predict the redox potentials and concomitant complex stability. It is shown that the main contribution emerges from the electrostatic interaction energy, and the partial charges of the pyridine donor groups therefore also correlate with the redox potentials

Synthesis and Reactivity of Cyclometalated Triamidophosphine Complexes of Niobium and Tantalum

The triamidophosphine protioligand <b>1</b> reacts with the homoleptic pentakis­(dimethylamido) precursors of niobium and tantalum [M­(NMe₂)₅, where M = Nb, Ta] to form cyclometalated complexes of the type [N₂PCN-κ⁵-<i>N</i>,<i>N</i>,<i>P</i>,<i>C</i>,<i>N</i>]­M­(NMe₂) (<b>2-M</b>). Apart from the three amido donors, one benzylic position of the ligand backbone is deprotonated over the course of this reaction, resulting in the formation of a new M–C bond. As a consequence, a metallaziridine substructure is formed, and the triamidophosphine moiety thus serves as a tetraanionic pentadentate ligand. The dimethylamido complexes <b>2-M</b> can be converted into the corresponding triflates [N₂PCN-κ⁵-<i>N</i>,<i>N</i>,<i>P</i>,<i>C</i>,<i>N</i>]­M­(OTf) (<b>3-M</b>) and alkyl complexes [N₂PCN-κ⁵-<i>N</i>,<i>N</i>,<i>P</i>,<i>C</i>,<i>N</i>]­M­(CH₂SiMe₃) (<b>4-M</b>) by treatment with triethylsilyl triflate (Et₃SiO₃SCF₃) followed by (trimethylsilyl)­methyllithium (LiCH₂SiMe₃). The alkyl complexes exhibit interesting reactivities, including a second cyclometalative backbone activation affording the trimethylphosphine-stabilized complexes [NP­(CN)₂-κ⁶-<i>N</i>,<i>P</i>,<i>C</i>,<i>N,C</i>,<i>N</i>]­M­(PMe₃) (<b>5-M</b>). In the case of tantalum, the formation of a dinuclear hydrido complex (<b>6</b>) is observed upon hydrogenation of <b>4-Ta</b>. In the case of niobium, the metallaziridine substructure in <b>4-Nb</b> is prone to ring opening via protonation with triphenylsilylamine (Ph₃SiNH₂), resulting in formation of the corresponding imido complex [PN₃<i>-κ</i>⁴-<i>P</i>,<i>N</i>,<i>N</i>,<i>N</i>]­NbNSiPh₃ (<b>7</b>)

A Novel Trisamidophosphine Ligand and Its Group(IV) Metal Complexes

A novel trisamidophosphine ligand scaffold has been synthesized and employed to coordinate all of the group­(IV) metals. The resulting complexes feature closed half-cage geometries with the phosphorus donor and all three amides binding to the metal. Out of nine complexes of the type [PN₃]­MX (M = Ti, Zr, Hf; X = NMe₂, OTf, CH₃), the zirconium derivatives have been studied by X-ray diffraction and shown to exhibit metal–phosphorus distances that are well in range of a coordinative bond. In contrast to its heavier homologues, the titanium methyl species [PN₃]­TiMe is prone to thermally induced ligand CH activation with concomitant loss of methane

Tuning of the Properties of Transition-Metal Bispidine Complexes by Variation of the Basicity of the Aromatic Donor Groups

Bispidines (3,7-diazabicyclo[3.3.1]­nonanes) as very rigid and highly preorganized ligands find broad application in the field of coordination chemistry, and the redox potentials of their transition-metal complexes are of importance in oxidation reactions by high-valent iron complexes, aziridination catalyzed by copper complexes, and imaging by ⁶⁴Cu positron emission tomography tracers. Here, we show that the redox potentials and stability constants of the copper­(II) complexes of 15 tetradentate bispidines can be varied by substitution of the pyridine rings (variation of the redox potential over ca. 450 mV and of the complex stability over approximately 10 log units). It is also shown that these variations are predictable by the p<i>K</i>_a values of the pyridine groups as well as by the Hammett parameters of the substituents, and the density functional theory based energy decomposition analysis also allows one to accurately predict the redox potentials and concomitant complex stability. It is shown that the main contribution emerges from the electrostatic interaction energy, and the partial charges of the pyridine donor groups therefore also correlate with the redox potentials

Tuning of the Properties of Transition-Metal Bispidine Complexes by Variation of the Basicity of the Aromatic Donor Groups

Bispidines (3,7-diazabicyclo[3.3.1]­nonanes) as very rigid and highly preorganized ligands find broad application in the field of coordination chemistry, and the redox potentials of their transition-metal complexes are of importance in oxidation reactions by high-valent iron complexes, aziridination catalyzed by copper complexes, and imaging by ⁶⁴Cu positron emission tomography tracers. Here, we show that the redox potentials and stability constants of the copper­(II) complexes of 15 tetradentate bispidines can be varied by substitution of the pyridine rings (variation of the redox potential over ca. 450 mV and of the complex stability over approximately 10 log units). It is also shown that these variations are predictable by the p<i>K</i>_a values of the pyridine groups as well as by the Hammett parameters of the substituents, and the density functional theory based energy decomposition analysis also allows one to accurately predict the redox potentials and concomitant complex stability. It is shown that the main contribution emerges from the electrostatic interaction energy, and the partial charges of the pyridine donor groups therefore also correlate with the redox potentials

Tuning of the Properties of Transition-Metal Bispidine Complexes by Variation of the Basicity of the Aromatic Donor Groups

Bispidines (3,7-diazabicyclo[3.3.1]­nonanes) as very rigid and highly preorganized ligands find broad application in the field of coordination chemistry, and the redox potentials of their transition-metal complexes are of importance in oxidation reactions by high-valent iron complexes, aziridination catalyzed by copper complexes, and imaging by ⁶⁴Cu positron emission tomography tracers. Here, we show that the redox potentials and stability constants of the copper­(II) complexes of 15 tetradentate bispidines can be varied by substitution of the pyridine rings (variation of the redox potential over ca. 450 mV and of the complex stability over approximately 10 log units). It is also shown that these variations are predictable by the p<i>K</i>_a values of the pyridine groups as well as by the Hammett parameters of the substituents, and the density functional theory based energy decomposition analysis also allows one to accurately predict the redox potentials and concomitant complex stability. It is shown that the main contribution emerges from the electrostatic interaction energy, and the partial charges of the pyridine donor groups therefore also correlate with the redox potentials

A Novel Trisamidophosphine Ligand and Its Group(IV) Metal Complexes

A novel trisamidophosphine ligand scaffold has been synthesized and employed to coordinate all of the group­(IV) metals. The resulting complexes feature closed half-cage geometries with the phosphorus donor and all three amides binding to the metal. Out of nine complexes of the type [PN₃]­MX (M = Ti, Zr, Hf; X = NMe₂, OTf, CH₃), the zirconium derivatives have been studied by X-ray diffraction and shown to exhibit metal–phosphorus distances that are well in range of a coordinative bond. In contrast to its heavier homologues, the titanium methyl species [PN₃]­TiMe is prone to thermally induced ligand CH activation with concomitant loss of methane

Tuning of the Properties of Transition-Metal Bispidine Complexes by Variation of the Basicity of the Aromatic Donor Groups

Bispidines (3,7-diazabicyclo[3.3.1]­nonanes) as very rigid and highly preorganized ligands find broad application in the field of coordination chemistry, and the redox potentials of their transition-metal complexes are of importance in oxidation reactions by high-valent iron complexes, aziridination catalyzed by copper complexes, and imaging by ⁶⁴Cu positron emission tomography tracers. Here, we show that the redox potentials and stability constants of the copper­(II) complexes of 15 tetradentate bispidines can be varied by substitution of the pyridine rings (variation of the redox potential over ca. 450 mV and of the complex stability over approximately 10 log units). It is also shown that these variations are predictable by the p<i>K</i>_a values of the pyridine groups as well as by the Hammett parameters of the substituents, and the density functional theory based energy decomposition analysis also allows one to accurately predict the redox potentials and concomitant complex stability. It is shown that the main contribution emerges from the electrostatic interaction energy, and the partial charges of the pyridine donor groups therefore also correlate with the redox potentials

Ditopic N‑Heterocyclic Pincer Carbene Complexes Containing a Perylene Backbone

A new class of ditopic perylene-based N-heterocyclic pincer ligands, tetrakis­(phosphinomethyl)-1,2,3,8,9,10-hexahydro­benzo­[1,2,3-<i>gh</i>:4,5,6-<i>g</i>′<i>h</i>′]­diperimidine derivatives (TPHDP), were synthesized via a one-pot reaction from 3,4,9,10-tetraaminoperylene either directly with the corresponding phosphine and paraformaldehyde or with the phosphonium salt and triethylamine as base. In this way the diphenyl-, dicyclohexyl-, and isopropylphosphinomethyl-functionalized protioligands were obtained (<b>1a</b>–<b>1c</b>). Reaction of <b>1a</b>–<b>1c</b> with [RhCl­(PPh₃)₃] led to a double geminal C–H activation and coordination of the ditopic PCP pincer to the rhodium centers, yielding the rhodium­(I)­chloro complexes (<b>2a</b>–<b>2c</b>) of all three ligands. These were found to be suitable starting materials for further ligand exchange of the chloride. Reaction with lithium phenylacetylide or the abstraction of the chloride ligand with thallium­(I) hexafluorophosphate in the presence of neutral donors gave the corresponding alkynyl complexes <b>3a</b> and <b>3b</b> or the ionic complexes [Rh­(Ph₃P)]₂-Ph-TPHDP (<b>4a</b>) and [Rh­(C₅H₅N)]₂-ⁱPr-TPHDP (<b>4b</b>). The most characteristic feature in the absorption spectra of all compounds is the intense band of the π* ← π transition of the aromatic (perylene) core with its partially resolved vibrational progression. The fluorescence quantum yields (ϕ) of compounds <b>1a</b>–<b>1c</b> were found to be between 72% and 86%. Upon coordination to rhodium, the intraligand transition in the absorption spectra is only slightly shifted, whereas the fluorescence is almost completely quenched