Desenvolvimento de moléculas bifuncionais a partir de ácidos graxos contendo N-heterocíclicos para formação de complexos de rutênio e de olefinas cíclicas para polimerizações via ROMP

Nenhuma Miniatura disponível
Data
2020-07-03
Autores
Título da Revista
ISSN da Revista
Título de Volume
Editor
Resumo

<span style="font-weight: 400;">Novos ligantes foram sintetizados utilizando 4-aminopiridina (py-4NH<span style="font-weight: 400;">2<span style="font-weight: 400;">), 3-aminopiridina (py-3NH<span style="font-weight: 400;">2<span style="font-weight: 400;">) e 1,10-fenantrolina-5-amino (phen-5NH<span style="font-weight: 400;">2<span style="font-weight: 400;">) como fonte de N-heterocíclicos. Para reagir com o grupo NH<span style="font-weight: 400;">2<span style="font-weight: 400;"> dos N-heterocíclicos foi utilizado como fonte de ácido graxo o óleo de girassol (G) e o ácido oleico (O) comercial. Como fonte de olefina cíclica <span style="font-weight: 400;">o ácido-5-norborneno-2- carboxílico (NBE-COOH). O cloreto de acila formado através de uma reação de acilação reagiu com o grupo NH<span style="font-weight: 400;">2<span style="font-weight: 400;"> para formar os ligantes piridina-3amida ácido graxo girassol (py-3NH-G), piridina-4amida ácido graxo girassol (py-4NH-G), piridina-3amida ácido graxo oleico (py-3NH-O), 1,10-fenantrolina-5amida ácido graxo oleico (phen-5NH-O) e 1,10-fenantrolina-5amida norborneno (phen-5NH-NBE). As purificações foram realizadas através de colunas de sílica gel. Todas as etapas para preparações dos ligantes foram caracterizadas por RMN de <span style="font-weight: 400;">1<span style="font-weight: 400;">H e FTIR. Esses ligantes foram utilizados nas novas sínteses de complexos com rutênio. Os complexos precursores [RuCl<span style="font-weight: 400;">2<span style="font-weight: 400;">(bpy)<span style="font-weight: 400;">2<span style="font-weight: 400;">].H<span style="font-weight: 400;">2<span style="font-weight: 400;">O, [RuCl<span style="font-weight: 400;">2<span style="font-weight: 400;">(phen)<span style="font-weight: 400;">2<span style="font-weight: 400;">].H<span style="font-weight: 400;">2<span style="font-weight: 400;">O e os complexos [RuCl(bpy)<span style="font-weight: 400;">2<span style="font-weight: 400;">(py-3NH-G)]PF<span style="font-weight: 400;">6<span style="font-weight: 400;">(complexo 1), [RuCl(bpy)<span style="font-weight: 400;">2<span style="font-weight: 400;">(py-4NH-G)]PF<span style="font-weight: 400;">6<span style="font-weight: 400;"> (complexo 2), [RuCl(bpy)<span style="font-weight: 400;">2<span style="font-weight: 400;">(py-3NH-O)]PF<span style="font-weight: 400;">6<span style="font-weight: 400;"> (complexo 3), [Ru(bpy)<span style="font-weight: 400;">2<span style="font-weight: 400;">(py-3NH-O)(py-3NH<span style="font-weight: 400;">2<span style="font-weight: 400;">)](PF<span style="font-weight: 400;">6<span style="font-weight: 400;">)<span style="font-weight: 400;">2<span style="font-weight: 400;"> (complexo 4), <span style="font-weight: 400;">[Ru(phen)<span style="font-weight: 400;">2<span style="font-weight: 400;">(phen-5NH-O)](PF<span style="font-weight: 400;">6<span style="font-weight: 400;">)<span style="font-weight: 400;">2<span style="font-weight: 400;">  (complexo 5) e [Ru(phen-5NH-O)<span style="font-weight: 400;">2<span style="font-weight: 400;">(phen-5NH-NBE)](PF<span style="font-weight: 400;">6<span style="font-weight: 400;">)<span style="font-weight: 400;">2<span style="font-weight: 400;">   (complexo 6) foram  sintetizados e caracterizados por RMN de <span style="font-weight: 400;">1<span style="font-weight: 400;">H , FTIR, voltametria cíclica e espectrofotometria UV-Vis. Nas purificações dos complexos derivados do precursor [RuCl<span style="font-weight: 400;">2<span style="font-weight: 400;">(bpy)<span style="font-weight: 400;">2<span style="font-weight: 400;">].H<span style="font-weight: 400;">2<span style="font-weight: 400;">O foram necessários o uso da coluna de sílica gel. Os complexos 1, 2, 3 e 4 foram irradiados em solução de acetonitrila e os novos ligantes sintetizados nesse trabalho foram substituídos. Com o complexo 6 e norborneno foi possível formar o polinorborneno com o metalomonômero ligado à cadeia. Esse polímero foi caracterizado por espectrofotometria UV-Vis, fluorimetria, GPC e TGA. <span style="font-weight: 400;">Obteve-se M<span style="font-weight: 400;">w<span style="font-weight: 400;"> = 3,7x10<span style="font-weight: 400;">5<span style="font-weight: 400;"> g/mol e IPD = 2,3 ± 0,2, com  estabilidade térmica até 250 °C<span style="font-weight: 400;">. O polímero manteve as características físicas e químicas do polinorborneno e do metalomonômero. 


<span style="font-weight: 400;">New ligands have been synthesized using 4-aminopyridine (py-4NH<span style="font-weight: 400;">2<span style="font-weight: 400;">), 3-aminopyridine (py-3NH<span style="font-weight: 400;">2<span style="font-weight: 400;">) and 1,10-phenanthroline-5-amino (phen-5NH<span style="font-weight: 400;">2<span style="font-weight: 400;">) as a source of N-heterocyclics. To react with the NH<span style="font-weight: 400;">2 <span style="font-weight: 400;">group of N-heterocyclics, sunflower (G) and oleic (O) oils were used as fatty acid  sources and 5-norbornene-2-carboxylic acid (NBE-COOH) as a source of cyclic olefin. The acylchloride formed through an acylation reaction reacted with the NH<span style="font-weight: 400;">2 <span style="font-weight: 400;">group to form the sunflower fatty acid (py-3NH-G), pyridine-4amide sunflower fatty acid (py-4NH-G), pyridine- 3amide oleic fatty acid (py-3NH-O), 1,10-phenanthroline-5amide oleic fatty acid (phen-5NH-O) and 1,10-phenanthroline-5amide norbornene (phen-5NH-NBE).  Purifications were performed using silica gel columns. All steps for preparing the ligands were characterized by <span style="font-weight: 400;">1<span style="font-weight: 400;">H NMR and FTIR. These ligands were used in the new synthesis of complexes with ruthenium. The precursor complexes [RuCl<span style="font-weight: 400;">2<span style="font-weight: 400;">(bpy)<span style="font-weight: 400;">2<span style="font-weight: 400;">].H<span style="font-weight: 400;">2<span style="font-weight: 400;">O, [RuCl<span style="font-weight: 400;">2<span style="font-weight: 400;">(phen)<span style="font-weight: 400;">2<span style="font-weight: 400;">].H<span style="font-weight: 400;">2<span style="font-weight: 400;">O and the complexes [RuCl(bpy)<span style="font-weight: 400;">2<span style="font-weight: 400;">(py-3NH-G)]PF<span style="font-weight: 400;">6 <span style="font-weight: 400;">(complex 1), [RuCl(bpy)<span style="font-weight: 400;">2<span style="font-weight: 400;">(py-4NH-G)]PF<span style="font-weight: 400;">6<span style="font-weight: 400;"> (complex 2), [RuCl(bpy)<span style="font-weight: 400;">2<span style="font-weight: 400;">(Py-3NH-O)]PF<span style="font-weight: 400;">6<span style="font-weight: 400;"> (complex 3), [Ru(bpy)<span style="font-weight: 400;">2<span style="font-weight: 400;">(py-3NH-O)(py-3NH<span style="font-weight: 400;">2<span style="font-weight: 400;">)](PF<span style="font-weight: 400;">6<span style="font-weight: 400;">)<span style="font-weight: 400;">2<span style="font-weight: 400;"> (complex 4), [Ru(phen)<span style="font-weight: 400;">2<span style="font-weight: 400;">(phen-5NH-O)](PF<span style="font-weight: 400;">6<span style="font-weight: 400;">)<span style="font-weight: 400;">2<span style="font-weight: 400;"> (complex 5) and [Ru(phen-5NH-O)<span style="font-weight: 400;">2<span style="font-weight: 400;">(phen-5NH-NBE)](PF<span style="font-weight: 400;">6<span style="font-weight: 400;">)<span style="font-weight: 400;">2<span style="font-weight: 400;">  (complex 6) were synthesized and characterized by 1H NMR, FTIR, cyclic voltammetry and UV-Vis spectrophotometry. In the purifications of the complexes derived from the precursor [RuCl<span style="font-weight: 400;">2<span style="font-weight: 400;">(bpy)<span style="font-weight: 400;">2<span style="font-weight: 400;">].H<span style="font-weight: 400;">2<span style="font-weight: 400;">O, the use of the silica gel column was necessary .Complexes 1, 2, 3 and 4 were irradiated in acetonitrile solution and the new ligands synthesized in this work were replaced. With complex 6 and norbornene, it was possible to form the polynorbornene with the metallomonomer attached to the chain. This polymer was characterized by UV-Vis spectrophotometry, fluorimetry, GPC and TGA. <span style="font-weight: 400;">M<span style="font-weight: 400;">w<span style="font-weight: 400;"> = 3.7x10<span style="font-weight: 400;">5<span style="font-weight: 400;"> g /mol and IPD = 2.3 ± 0.2 were obtained, with thermal stability up to 250 °C. <span style="font-weight: 400;">The polymer maintained the physical and chemical characteristics of the polynorbornene and the metallomer.

Descrição
Palavras-chave
ácidos graxos, moléculas bifuncionais, ROMP, rutênio, bifunctional molecules, fatty acids, ROMP, ruthenium
Citação