Complexos de base schiff de rutênio(lll): preparação, caracterização, e avaliação como potenciais sistemas P450-bioinspirados

Abstract

Brazil is one of the countries with the highest agrochemical’s consumption, highlighting the Simazina, an herbicide of the triazine class. Besides it being harmful to directly exposed humans also is responsible for several damages to the environment, specifically water sources. Therefore, it is necessary to research oxidation of this molecule, in order to provide a better base of toxicological profile as well as to assist in the remediation of systems that are affected by this pesticide. In living systems, the superfamily of enzymes performs the metabolism of exogenous molecules (pesticides, dyes and drugs) are the Cytochromes P450. These monoxygenases perform the biotransformation of substrates in a fast, versatile and high effective way, thus use of synthetic model-systems that mimics the catalytic function of P450 has been studied over the past three decades. In this context, the objective of this work was synthesize, characterize and evaluate the catalytic activity of P450 in ruthenium salen complexes at Simazine oxidation. Compounds of iron and manganese with salen were also synthesized to constrast with ruthenium complexes, [RuNOCl(Salen-N(Et)2)], [MnCl(Salen-N(Et)2)], [FeCl(Salen-N(Et)2)], [RuNOCl(Salen-MeCl)] and [MnCl(Salen- MeCl)]. These coordination compounds were characterized by spectral techniques (FTIR and UV-Vis) and electrochemical (cyclic voltammetry). The efficiency of the complexation was indicated by the analyzes as well as the high-transition states of the metals that possibly act in bioinspired oxidative reaction mechanism. The catalytic assays of these complexes in the Simazine oxidation were performed with the respective oxygen donors: H2O2, PhIO, NaClO and m-CPBA and the products were separated by HPLC. The catalysts obtained satisfactory results of substrate conversion, particularly for [Ru(Salen-MeCl)]/NaClO system which achieved 26.4%. Regarding the product distribution, the most selective catalyst was the [Ru (Salen-N (Et) 2)] as result of it was presented only two products in the presence of all oxidants.