Browsing by Author "Henríquez Toro, Marco Antonio"

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    Design and synthesis of new copper complexes bearing N,N – heterocyclic derivatives ligands – Potential active photoredoxcatalyst for organic transformations
    (2022) Henríquez Toro, Marco Antonio; Cabrera Caballero, Alan Raúl; Pontificia Universidad Católica de Chile. Escuela de Química
    In this work, five new heteroleptic CuI complexes (C1-5) of the type [Cu(dpa)(P,P)]BF4 based on dipyridylamine (dpa) as N,N ligand and commercial diphosphines ligands have been synthesised through a simple methodology with high yields. All complexes were thoroughly characterised by spectroscopic and spectrometric techniques, as well by theoretical calculations. These showed MLCT absorptions in the 300–370 nm region and emission in the 450–520 nm region with quantum yields and lifetimes that depend on the nature of the P,P ligand. The photocatalytic performance of CuI complexes C1-5 were evaluated for their use as photoredox catalysts in ATRA reactions, decarboxylative coupling and an Appel-type reaction. The use of readily available dpa as N,N ligand constitutes an attractive alternative to the well-established phenanthroline ligands typically used in photocatalysis. Additionally, modifications of the dpa ligand were explored without good positive results. On the other hand, six CuII complexes (C6-12) were synthesized and evaluated in two reactions. Unfortunately, the results did not exceed the yields reported by Cu(dap) Cl2 and [Cu(dmp)2Cl]Cl. Csp3 -sp coupling by copper and light was explored using two strategies. (1) Using the CuI -phenylacetylide species and N-alkoxyphtalimides or alkyl Katryzky salt as a radical source. In this case, the coupling product was obtained in 52 % of yield. However, we decided to explore a more challenging route, (2) Using HAT as a way to generate alkane radicals, using a mixture of Cu (OAc)2 and oxidant as reaction initiators. Unfortunately, in this last strategy, the performance did not exceed the 26 % yield. Finally, preliminary studies for the multicomponent aminosulfonylation of styrene reaction were developed; the reaction optimization was done, and 83 % yield of the product was obtained using tosyl chloride, carbazole and styrene.
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    Heteroleptic Cu(i) complexes bearing methoxycarbonyl-imidoylindazole and POP ligands-an experimental and theoretical study of their photophysical properties
    (2018) González Pavez, Iván Alonso; Henríquez Toro, Marco Antonio; Cortés Arriagada, Diego; Natali, Mirco; Daniliuc, Constantin G.; Dreyse, Paulina A.; Maze Ríos, Jerónimo; Rojas Guerrero, René; Salas Sánchez, Cristián Osvaldo; Cabrera Caballero, Alan Raúl