Computational chemistry has gained interest as a characterization tool to predict photoluminescence, reactivity and structural properties of organic and transition metal complexes. With the rise of methods including relativity, these studies have been expanded to the accurate modeling of luminescence spectra of complexes with considerable spin-orbit splitting due to heavy metal centers as well as the reaction pathways for these complexes to produce natural products such as hydrogen gas. These advances have led to the synthesis and utility of more effective catalysis as well as the development of more effective organic light emitting diodes (OLEDs) through the incorporation of organometallic complexes as emitters instead of typical organic emitters. In terms of significant scientific advancement presented in this work is in relation to the discovery of significant spin-orbit splitting in a gold(I) alkylphosphine complex, where the splitting results in the states that emit in different colors of the visible region of the electromagnetic spectrum. This work also reveals the discovery both computationally and experimentally, of a genuine polar-covalent bond between two-closed shell metals. This work highlights a complex with an incredibly short gold(I) – copper(I) intermetallic distance leading to a vibrational frequency and dissociation energy that is on par with those of other systems with single-bonded metal centers. Lastly, this work outlines a strategy for the production of hydrogen gas through the use of trinuclear cyclic coinage metal complexes as catalysis to split hydrohalic acids.

This thesis is focused on the unexplored field of organometallic copper(III) chemistry. Arylcopper(III) complexes have been proposed as key intermediates in Ullmann condensation reactions that consist in the coupling of aryl halides and heteroatom nucleophiles catalyzed by copper. The study of the reactivity of well-defined arylcopper(III) complexes may provide a better understanding of the mechanism of Ullmann condensation reactions, which is still under intense debate. In this doctoral dissertation we study the feasibility of well-defined arylcopper(III) complexes, which are stabilized within macrocyclic ligands, to participate in C-heteroatom bond forming reactions. We develop copper-catalyzed C-N and C-O bond forming reactions, as well halide exchange reactions, including fluorinations, based on Cu(I)/Cu(III) catalytic cycle within model aryl halide substrates. We uncover the fundamental understanding of the two-electron redox steps, oxidative addition and reductive elimination, at copper. / Aquesta tesi es centra en el camp de la química organometàl•lica del coure(III) que roman sense explorar. Els complexos arilcoure(III) s'han proposat com a intermedis clau en les reaccions de condensació Ullmann que consisteixen en l'acoblament d'halurs d'arils i nucleòfils basats en heteroàtoms catalitzades amb coure. L'estudi de la reactivitat de complexos arilcoure(III) ben definits pot proporcionar una millor comprensió del mecanisme de les reaccions de condensació Ullmann, el qual es troba sota un intens debat. En aquesta tesi doctoral s'estudia la viabilitat del complexos arilcoure(III), estabilitzats en lligands macrocíclics, de participar en reaccions de formació d'enllaç carboni-heteroàtom. S'han desenvolupat reaccions de formació d'enllaç C-N i C-O així com reaccions d'intercanvi d'halurs, on s'inclouen fluoracions, catalitzades amb coure i basades en un cicle catalític Cu(I)/Cu(III) utilitzant substrats models d'halur d'aril. S'ha obtingut una comprensió fonamental de les etapes redox a dos electrons, addició oxidant i eliminació reductiva, en coure.