Durante este trabajo de tesis se sintetizaron y caracterizaron dos nuevos tiosacarinatos iónicos y 33 nuevos tiosacarinatos coordinados a metales del grupo 11, Cu(I), Ag(I) y Au(I). Se obtuvieron complejos binarios y ternarios, usando coligandos nitrogenados, fosforados y azufrados. Los compuestos obtenidos se caracterizaron realizando análisis elemental, IR, Raman, UV-Visible, RMN de 1H, 13C y 31P y fueron determinadas las estructuras cristalinas por difracción de Rayos-X de monocristal en los casos en los que fue posible: PNP(tsac), [Ag6(tsac)6], [Ag2(tsac)2]n, [Ag2(tsac)2]n1,5DMF, [Ag2(tsac)2(2,2-bipi)2], [Ag(tsac)(o-fen)]n , [Ag(tsac)(2,2-biquin)], [Ag2(tsac)2(quin)2], [Ag2(tsac)2(pi)], [Ag2(tsac)2(4-Mepi)]n, [Ag(tsac)(3-Mepi)2]n, [Ag(tsac)(4-MeOpi)]n , [Ag(tsac)(PPh3)2], [Ag(tsac)(PPh3)3], [Ag4(tsac)4(PPh3)3], [Ag4(tsac)4(PPh3)4], [Ag(tsac)(dppe)CH3CN]n, [Cu4(tsac)4(CH3CN)2]2CH3CN, [Cu(tsac)(PPh3)2], [Cu4(tsac)4(PPh3)3]CH3CN, [Cu4(tsac)4(dppm)2]CH2Cl2, [Cu2(tsac)2(dppm)2]2CH2Cl2, [{Cu(tsac)(dppe)}2-μ-dppe)]4CH3CN, [Cu2(tsac)2(Sbim)2CH3CN], [Au(tsac)(PPh3)] y [Au2(tsac)2(dppm)]EtOH. Se obtuvieron como productos microcristalinos o como polvos los compuestos NBu4(tsac), Ag2(tsac)2(dppm)3, Au2(tsac)2(dppe), Au(tsac)(Htsac)2, Cu(tsac)(tu), Cun(tsac)n(dmpyz)n, Cu(tsac)(pyz)0,25, Cu(tsac)(4,4-bipi)0,375, Cu(tsac)(4,4-bipi)0,75 En todos los casos se analizó la coordinación del anión a los centros metálicos y los entornos de coordinación del metal.
Se estudiaron los complejos [Ag2(tsac)2], [Ag2(tsac)2(pi)], [Ag2(tsac)2(2,2-bipi)2], [Au2(tsac)2(dppm)] y los modelos hipotéticos de tipo [Ag2(tsac)2(R-pi)] y [Ag2(tsac)2(quin)] (R = H, 4-Me, 4-CN, 4-MeO, 4-CF3, 4-OH, 4-F, 4-Cl y 4-NO2) de manera teórica, utilizando la Teoría del Funcional de la Densidad con el programa Gaussian 03. Para algunos casos seleccionados también se aplicó el método MP2, incluido en el mencionado programa. Se analizó la interacción plata-plata en los complejos [Ag2(tsac)2], [Ag2(tsac)2(pi)], [Ag2(tsac)2(2,2-bipi)2] y también en los sistemas hipotéticos mencionados anteriormente. En el complejo [Au2(tsac)2(dppm)] se analizó la interacción Au-Au utilizando la misma metodología. Las asignaciones de las frecuencias de vibración de los complejos se realizaron utilizando las frecuencias calculadas para la Htsac, para el anión tsac y para los complejos [Ag2(tsac)2], [Ag2(tsac)2(pi)] y [Ag2(tsac)2(2,2-bipi)2]. / During this thesis two new ionic thiosaccharinates and 33 new thiosaccharinates with group 11 metals, Cu(I), Ag(I) and Au(I) have been synthesized and fully characterized. Binary and ternary complexes have been obtained, using coligands with nitrogen, sulfur and phosphorous as donor atoms. The obtained compounds have been characterized by elemental analysis, IR, Raman, UV-Visible, 1H, 13C and 31P NMR. When possible, single crystal X-ray diffraction studies have been made to solve crystal structures: PNP(tsac), [Ag6(tsac)6], [Ag2(tsac)2]n, [Ag2(tsac)2]n1,5DMF, [Ag2(tsac)2(2,2-bipi)2], [Ag(tsac)(o-fen)]n, [Ag(tsac)(2,2-biquin)], [Ag2(tsac)2(quin)2], [Ag2(tsac)2(pi)], [Ag2(tsac)2(4-Mepi)]n, [Ag(tsac)(3-Mepi)2]n, [Ag(tsac)(4-MeOpi)]n, [Ag(tsac)(PPh3)2], [Ag(tsac)(PPh3)3], [Ag4(tsac)4(PPh3)3], [Ag4(tsac)4(PPh3)4], [Ag(tsac)(dppe)(CH3CN)], [Cu4(tsac)4(CH3CN)2]2CH3CN, [Cu(tsac)(PPh3)2], [Cu4(tsac)4(PPh3)3]CH3CN, [Cu4(tsac)4(dppm)2]CH2Cl2, [Cu2(tsac)2(dppm)2]2CH2Cl2, [{Cu(tsac)(dppe)}2-μ-dppe)]4CH3CN [Cu2(tsac)2(Sbim)2CH3CN], [Au(tsac)(PPh3)], [Au2(tsac)2(dppm)]EtOH. As microcrystalline compounds or powder NBu4(tsac), Ag2(tsac)2(dppm)3, Au2(tsac)2(dppe), Au(tsac)(Htsac)2, Cu(tsac)(tu), Cun(tsac)n(dmpyz)n, Cu(tsac)(pyz)0,25, Cu(tsac)(4,4-bipi)0,375, Cu(tsac)(4,4-bipi)0,75 have been obtained. The coordination modes of the thiosaccharinate anion and the geometries of the metal environments were analyzed.
The complexes [Ag2(tsac)2], [Ag2(tsac)2(pi)], [Ag2(tsac)2(2,2-bipi)2] and [Au2(tsac)2(dppm)] and some hypothetical models as [Ag2(tsac)2(R-pi)] ( R = H, 4-Me, 4-CN, 4-MeO, 4-CF3, 4-OH, 4-CF3, 4-F and 4-NO2) were theoretically studied, using the Density Functional Theory with the program Gaussian 03. For some selected examples, the method MP2 included in the mentioned program was also applied. The results support the existence of silver-silver interactions in the dimers [Ag2(tsac)2], [Ag2(tsac)2(pi)] and [Ag2(tsac)2(2,2-bipi)2] and aurophilic interaction in [Au2(tsac)2dppm]. The vibrational frequency assignations were done using the calculated frequencies for Htsac, for the anion tsac and for the complexes [Ag2(tsac)2], [Ag2(tsac)2(pi)] y [Ag2(tsac)2(2,2-bipi)2].
| Identifer | oai:union.ndltd.org:uns.edu.ar/oai:repositorio.bc.uns.edu.ar:123456789/1953 |
| Date | 09 December 2009 |
| Creators | Dennehy, Mariana |
| Contributors | Quinzani, Oscar V. |
| Publisher | Universidad Nacional del Sur |
| Source Sets | Universidad Nacional del Sur |
| Language | Spanish |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation, Text |
| Rights | 0 |
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