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franchi_sjs_dr_araiq.pdf: 5568968 bytes, checksum: 8306343e54141c16774212c039fd5233 (MD5) / O presente trabalho teve como objetivo a síntese de compostos de paládio(II) utilizando como precursor o complexo [PdCl2(LH2)]×H2O (1), onde LH2 = 4,4’,5,5’-tetrametil-2,2’-bis-imidazol. A obtenção de novos derivados de Pd(II) a partir do composto 1 ocorreu empregando os sais KBr e KSCN, os ligantes sulfurados {tiouréia (tu); N-metiltiouréia (mtu); N-feniltiouréia (ftu); N,N’-dimetiltiouréia (dmtu); N,N’-difeniltiouréia (dftu)}, diimínicos {2,2’-bipiridina (bpy), 1,10-fenantrolina (phen); 1,10-fenantrolina- 5,6-diona (pheno)} e fosfínicos {1,2-bis(difenilfosfina)etano (dppe), cis-1,2-bis(difenilfosfina)etileno (dppet) e 1,3-bis(difenilfosfina)propano (dppp); trifenilfosfina (PPh3)}. Os compostos foram caracterizados por análise elementar, espectroscopia vibracional na região do infravermelho, ressonância magnética nuclear de 1H, 13C{1H}, MAS-RMN de 31P e por termogravimetria. As reações entre o precursor [PdCl2(LH2)] (1) e os sais KBr e KSCN conduziram a formação dos complexos [PdBr2(LH2)] (2) e [Pd2(g-1,3-SCN)2(SCN)2(LH2)] (3), respectivamente. A partir da análise dos dados espectroscópicos e dos resultados provenientes da otimização da geometria dos complexos utilizando a metodologia DFT, foi possível evidenciar o modo de coordenação quelante bidentado do ligante LH2 pelo deslocamento das bandas com forte contribuição do modo bNH em 1206 e 1379 cm-1 para frequências significativamente maiores que aquelas observadas no espectro no IV do ligante (1104 cm- 1 e 1353 cm-1, respectivamente). A presença de grupos tiocianatos coordenados no modo S-terminal e end-to-end no complexo 3 foi sugerida pelo aparecimentos de duas bandas nasSCN em 2160 e 2114 cm-1. Os complexos [Pd(tu)2(LH2)]Cl2 (4), [Pd(metu)2(LH2)]Cl2 (5), [Pd(ftu)2(LH2)]Cl2 (6), [Pd(dmtu)2(LH2)]Cl2 (7) e [Pd(dftu)2(LH2)]Cl2 (8)... / This work deals with the synthesis of Pd(II) compounds using [PdCl2(LH2)] (1), where LH2 = 4,4’,5,5’- tetramethyl-2,2’-bis-imidazole, as a precursor. New Pd(II) derivatives were prepared from the reaction between compound 1 and KBr and KSCN salts, sulfur-based ligands {thiourea (tu); N-methylthiourea (mtu); N-phenylthiourea (ptu); N,N’-dimethylthiourea (dmtu); N,N’-diphenylthiourea (dptu)}, diimines-type ligands {2,2’-bipyridine (bpy), 1,10-phenanthroline (phen); 1,10-phenanthroline-5,6-dione (pheno)} and phosphines {1,2-bis(diphenylphosphine)ethane (dppe), cis-1,2-bis(diphenylphosphine)ethylene (dppet) and 1,3-bis(diphenylphosphine)propane (dppp); triphenylphosphine (PPh3)}. The compounds were characterized by means of elemental analyses, IR spectroscopy, 1H, 13C{1H} NMR and 31P MAS-NMR spectroscopy and thermogravimetry. Reactions between [PdCl2(LH2)]×H2O (1) and the KBr and KSCN salts yielded the complexes [PdBr2(LH2)] (2) and [Pd2(g-1,3-SCN)2(SCN)2(LH2)] (3), respectively. From the inspection of spectroscopic data and results from geometry optimization of the complexes, calculated using the DFT/B3LYP method, the chelating bidentate coordination mode of the ligand was proposed by the shift to higher frequencies of the bNH bands at 1206 and 1379 cm-1 upon complexation (free ligand: 1104 cm-1 and 1353 cm-1). Complexes [Pd(tu)2(LH2)]Cl2 (4), [Pd(metu)2(LH2)]Cl2 (5), [Pd(ptu)2(LH2)]Cl2 (6), [Pd(dmtu)2(LH2)]Cl2 (7) and [Pd(dptu)2(LH2)]Cl2 (8) were synthesized from the reaction between 1 and the suitable thiourea type ligands, at the 1:2 molar ratio, respectively. Spectroscopic techniques provide useful information on the S-coordination mode of thioureas as well on the structural proposals. Reaction between precursor 1 and the diimines bpy, phen and pheno afforded the... (Complete abstract click electronic access below)
| Identifer | oai:union.ndltd.org:IBICT/oai:repositorio.unesp.br:11449/105781 |
| Date | 12 April 2013 |
| Creators | Franchi, Silmar José Spinardi [UNESP] |
| Contributors | Universidade Estadual Paulista (UNESP), Netto, Adelino Vieira de Godoy [UNESP] |
| Publisher | Universidade Estadual Paulista (UNESP) |
| Source Sets | IBICT Brazilian ETDs |
| Language | Portuguese |
| Detected Language | English |
| Type | info:eu-repo/semantics/publishedVersion, info:eu-repo/semantics/doctoralThesis |
| Format | 145 f. |
| Source | Aleph, reponame:Repositório Institucional da UNESP, instname:Universidade Estadual Paulista, instacron:UNESP |
| Rights | info:eu-repo/semantics/openAccess |
| Relation | -1, -1 |
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