A química de coordenação e reatividade dos complexos de zinco(II) contendo ligantes mono aniônicos hidrotris(pirazolil)borato substituídos por grupos 3,3,3 - mesitil (TpMs) e 3,3,5 - mesitil (TpMs*) foram investigadas. A metátese dos sais Tl[TpMs] ou Tl[TpMs*] com ZnCl2, ZnEt2, e Zn(OAc)2 permitiu a formação dos compostos correspondentes puros TpMsZnCl, TpMsZnEt, TpMs*ZnEt e TpMsZnOAc. O composto TpMs*ZnEt, lentamente, desproporcionou-se em solução de benzeno para produzir o complexo bis(ligante) (k²-TpMs*)2Zn. Alternativamente, o complexo TpMsZnOAc, como também TpMsZnOCOPh e [TpMs*ZnOAc]2 foram preparados por acidólise dos complexos análogos TpMsZnEt e TpMs*ZnEt com o correspondente ácido carboxílico. Não foi observada reação entre TpMsZnEt e TpMs*ZnEt com os álcoois (ROH; R = Me, Et, iPr, Bn), enquanto que as reações de metátese de Tl[TpMs] com ZnEt(OR) levaram à formação do complexo TpMsZnEt, ao invés do complexo desejado zinco-alcóxido. Compostos TpMsZnCl, TpMsZnEt, TpMs*ZnEt, TpMsZnOAc, TpMsZnOCOPh, [TpMs*ZnOAc]2 foram caracterizados por análise elementar, espectroscopia de RMN de ¹H e ¹³C, e TpMsZnCl, TpMsZnEt, TpMsZnOAc, (k²-TpMs*)2Zn e [TpMs*ZnOAc]2 por estudos de difração de raio-X. Os compostos TpMsZnCl, TpMsZnEt, TpMsZnOAc e (k²-TpMs*)2Zn adotaram uma estrutura monomérica no estado sólido enquanto que o composto [TpMs*ZnOAc]2 existe como um dímero em ponte anti-sin por grupos acetato. O complexo (k2-TpMs*)2Zn é tetracoordenado, representando um raro modo de coordenação bidentado dos ligantes TpMs*. Os resultados foram racionalizados em termos da restrição estérea, que envolve o átomo de zinco, causada pelos ligantes TpMs e TpMs*. / The coordination chemistry and reactivity of zinc(II) complexes supported by monoanionic hydrotris(pyrazolyl)borate ligands substituted by 3,3,3-mesityl groups (TpMs) and 3,3,5-mesityl groups (TpMs*) have been investigated. Salt metathesis of ZnCl2, ZnEt2, and Zn(OAc)2 with Tl[TpMs] or Tl[TpMs*] cleanly afforded the corresponding compounds TpMsZnCl, TpMsZnEt, TpMs*ZnEt and TpMsZnOAc. Compound TpMs*ZnEt slowly disproportionates in benzene solution to afford the bis(ligand) complex (k²-TpMs*)2Zn. Acetate complex TpMsZnOAc as well as TpMsZnOCOPh and [TpMs*ZnOAc]2 were alternatively prepared by acidolysis of the parent ethyl complexes with the corresponding carboxylic acid. No reaction was observed between TpMsZnEt and TpMs*ZnEt and alcohols (ROH; R = Me, Et, iPr, Bn), while salt metathesis reactions of ZnEt(OR) with Tl[TpMs] led to TpMsZnEt instead of the desired zincalkoxide complex. Compounds TpMsZnCl, TpMsZnEt, TpMs*ZnEt, TpMsZnOAc, TpMsZnOCOPh, [TpMs*ZnOAc]2 were characterized by elemental analysis, ¹H and ¹³C NMR spectroscopy, as well as by X-ray diffraction studies for TpMsZnCl, TpMsZnEt, TpMsZnOAc, (k²-TpMs*)2Zn and [TpMs*ZnOAc]2. The former compounds adopt a monomeric structure in the solid state while [TpMs*ZnOAc]2 exists as an anti-syn bridged acetate dimer. Complex (k2-TpMs*)2Zn is fourcoordinated, featuring a rare bidentate coordination mode of the TpMs* ligands. The results are rationalized in terms of the variable steric constraint around the zinc atom provided by the TpMs and TpMs* ligands.
| Identifer | oai:union.ndltd.org:IBICT/oai:lume.ufrgs.br:10183/172772 |
| Date | January 2009 |
| Creators | Klitzke, Joice Sandra |
| Contributors | Casagrande Júnior, Osvaldo de Lázaro |
| Source Sets | IBICT Brazilian ETDs |
| Language | Portuguese |
| Detected Language | English |
| Type | info:eu-repo/semantics/publishedVersion, info:eu-repo/semantics/masterThesis |
| Format | application/pdf |
| Source | reponame:Biblioteca Digital de Teses e Dissertações da UFRGS, instname:Universidade Federal do Rio Grande do Sul, instacron:UFRGS |
| Rights | info:eu-repo/semantics/openAccess |
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