{ "dc.contributor": "Universitat de Girona. Departament de Química" , "dc.contributor.author": "Duran i Carpintero, Josep" , "dc.date.accessioned": "2012-05-29T08:29:07Z" , "dc.date.available": "2012-05-29T08:29:07Z" , "dc.date.issued": "1999-07-22" , "dc.identifier.isbn": "8468812978" , "dc.identifier.other": "DL Gi.423-2002" , "dc.identifier.uri": "http://www.tdx.cat/TDX-0120103-113648" , "dc.identifier.uri": "http://hdl.handle.net/10803/8024" , "dc.identifier.uri": "http://hdl.handle.net/10256/4740" , "dc.description.abstract": "The oxidative addition proved to be a useful method to prepare platinum (II) hydridotiolate by reaction of tetrakis(triphenylphosphine)platinum(0) with aminothiolate and phosphinothiolate ligands like cysteamine, cysteine ethyl and methyl Esther, 2-(diphenylphosphino)ethanetiol and 2-(diphenylphosphino)propanetiol. The complexes are square-planar and the aminothiolate or phosphinothiolate ligands are chelated to platinum (II). The hydrido ligand is trans to the sulfur and the other coordination position is occuped by a triphenylphosphine ligand. The complexes are mononuclear and they show low symmetry. The only symmetry element, the plan is broke if the ligand is branched, obtaining asymmetric complexes C1. If the ligand has electronic or esteric impediments the reaction doesn't run and the starting products are recovered. This was observed with N,N-dimethylcysteamine and penicylamine methyl esther ligands. In the special case of orthoaminotiophenol the hydridotiolate was obtained but the ligand was not chelated. The aminothiolate complexes don't show solution equilibrium. Otherwise, the complexe with 2-(diphenylphosphino)ethanetiol show an isomerisation equilibrium which forms cis isomer as a minor component. The complexe with 2-(diphenylphosphino)-propanetiol shows a conformational equilibrium between chair and twist forms. The complexes have been tested as catalyst precursors in hydroformylation and hydrosilylation reactions. The hydroformylation reaction runs only in presence of SnCl2 as cocatalyst. Catalytic activity depends on the presence of triphenylphosphine and, with less magnitude, CO and H2 pressure. We also studied the enantioselectivity using a chiral complexe. In the hydrosililation reaction, catalysts run with good results (<90%) using triethylsilane as silicon hydride. Dehydrogenative addition product has been also found in this reaction." , "dc.format.mimetype": "application/pdf" , "dc.language.iso": "cat" , "dc.publisher": "Universitat de Girona" , "dc.rights": "ADVERTIMENT. L'accés als continguts d'aquesta tesi doctoral i la seva utilització ha de respectar els drets de la persona autora. Pot ser utilitzada per a consulta o estudi personal, així com en activitats o materials d'investigació i docència en els termes establerts a l'art. 32 del Text Refós de la Llei de Propietat Intel·lectual (RDL 1/1996). Per altres utilitzacions es requereix l'autorització prèvia i expressa de la persona autora. En qualsevol cas, en la utilització dels seus continguts caldrà indicar de forma clara el nom i cognoms de la persona autora i el títol de la tesi doctoral. No s'autoritza la seva reproducció o altres formes d'explotació efectuades amb finalitats de lucre ni la seva comunicació pública des d'un lloc aliè al servei TDX. Tampoc s'autoritza la presentació del seu contingut en una finestra o marc aliè a TDX (framing). Aquesta reserva de drets afecta tant als continguts de la tesi com als seus resums i índexs." , "dc.source": "TDX (Tesis Doctorals en Xarxa)" , "dc.subject": "Tesis i dissertacions acadèmiques" , "dc.subject.other": "Hidroformilació" , "dc.subject.other": "Platí" , "dc.subject.other": "Compostos complexos" , "dc.subject.other": "Catalitzadors" , "dc.subject.other": "Catalysts" , "dc.subject.other": "Fosfinotiols" , "dc.subject.other": "Síntesi asimètrica" , "dc.subject.other": "Asymmetric catalysis" , "dc.subject.other": "Platinum" , "dc.subject.other": "Compuestos complejos" , "dc.subject.other": "Hidroformilación" , "dc.subject.other": "Complex compounds" , "dc.subject.other": "Catalizadores" , "dc.subject.other": "Hydrosililation" , "dc.subject.other": "Hidrosililación" , "dc.subject.other": "Fosfinotioles" , "dc.subject.other": "Hydroformylation" , "dc.subject.other": "Phosphinothioles" , "dc.subject.other": "Síntesis asimétrica" , "dc.subject.other": "Platino" , "dc.subject.other": "Catálisi asimétrica" , "dc.subject.other": "Hidrosililació" , "dc.subject.other": "Asymmetric Synthesis" , "dc.subject.other": "Catàlisi asimètrica" , "dc.title": "Síntesi, caracterització i avaluació com a catalitzadors de nous complexos quirals de platí" , "dc.type": "info:eu-repo/semantics/doctoralThesis" , "dc.rights.accessRights": "info:eu-repo/semantics/openAccess" , "dc.contributor.director": "Real i Obradors, Juli" , "dc.contributor.director": "Polo Ortiz, Alfonso" , "dc.subject.udc": "546 - Química inorgànica" , "dc.type.version": "info:eu-repo/semantics/publishedVersion" }