abstract: The search for highly active, inexpensive, and earth abundant replacements for existing transition metal catalysts is ongoing. Our group has utilized several redox non-innocent ligands that feature flexible arms with donor substituents. These ligands allow for coordinative flexibility about the metal centre, while the redox non-innocent core helps to overcome the one electron chemistry that is prevalent in first row transition metals. This dissertation focuses on the use of Ph2PPrDI, which can adopt a κ4-configuration when bound to a metal. One reaction that is industrially useful is hydrosilylation, which allows for the preparation of silicones that are useful in the lubrication, adhesive, and cosmetics industries. Typically, this reaction relies on highly active, platinum-based catalysts. However, the high cost of this metal has inspired the search for base metal replacements. In Chapter One, an overview of existing alkene and carbonyl hydrosilylation catalysts is presented. Chapter Two focuses on exploring the reactivity of (Ph2PPrDI)Ni towards carbonyl hydrosilylation, as well as the development of the 2nd generation catalysts, (iPr2PPrDI)Ni and (tBu2PPrDI)Ni. Chapter Three presents a new C-O bond hydrosilylation reaction for the formation of silyl esters. It was found the (Ph2PPrDI)Ni is the most active catalyst in the literature for this transformation, with turnover frequencies of up to 900 h-1. Chapter Four explores the activity and selectivity of (Ph2PPrDI)Ni for alkene hydrosilylation, including the first large scope of gem-olefins for a nickel-based catalyst. Chapter Five explores the chemistry of (Ph2PPrDI)CoH, first through electronic structure determinations and crystallography, followed by an investigation of its reactivity towards alkyne hydroboration and nitrile dihydroboration. (Ph2PPrDI)CoH is the first reported cobalt nitrile dihydroboration catalyst. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2018

abstract: The late first row transition metals, being inexpensive and environmentally benign, have become very attractive for sustainable catalyst development. However, to overcome the detrimental one electron redox processes exhibited by these metals, the employment of redox non-innocent chelates turned out to be very useful. The Trovitch group has designed a series of pentadentate bis(imino)pyridine ligands (pyridine diimine, PDI) that are capable of binding the metal center beyond their 3-N,N,N core and also possess coordination flexibility. My research is focused on developing PDI-supported manganese catalysts for organic transformations and renewable fuel production. The thesis presents synthesis and characterization of a family of low valent (PDI)Mn complexes. Detailed electronic structure evaluation from spectroscopic and crystallographic data revealed electron transfer from the reduced metal center to the accessible ligand orbitals. One particular (PDI)Mn variant, (5-Ph2PPrPDI)Mn has been found to be the most efficient carbonyl hydrosilylation catalyst reported till date, achieving a maximum turnover frequency of up to 4950 min-1. This observation demanded a thorough investigation of the operative mechanism. A series of controlled stoichiometric reactions, detailed kinetic analysis, and relevant intermediate isolation suggest a mechanism that involves oxidative addition, carbonyl insertion, and reductive elimination. Noticing such remarkable efficiency of the (PDI)Mn system, it has been tested for application in renewable fuel generation. A modest efficiency for H2 production at an apparent pH of 8.4 have been achieved using a cationic Mn complex, [(Ph2PPrPDI)Mn(CO)]Br. Although, a detailed mechanistic investigation remained challenging due to complex instability, a set of relevant Mn(-I) intermediates have been isolated and characterized thoroughly. The dissertation also includes synthesis, characterization, and electronic structure evaluation of a series of Triphos supported iron complexes. Using this pincer chelate and either 2,2’-bipyridine (bpy) or 1,3,5,7-cyclooctatetraene (COT), a set of electronically interesting complexes have been isolated. Detailed electronic structure investigation using spectroscopy, magnetometry, crystallography, and DFT calculations revealed redox non-innocent behavior in the Bpy and COT ligands. Additionally, CO binding to the (Triphos)Fe system followed by reaction with borohydride reagents allowed for the isolation of some catalytically relevant and reactive iron hydride complexes. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2016

Les ligands phosphasalen développés au sein du laboratoire peuvent être considérés comme les analogues phosphorés des ligands salen dont ils diffèrent par la présence de groupements iminophosphorane à la place des imines. L’introduction de ces fonctions a d’importantes conséquences sur les propriétés de ces ligands, qui sont plus électrodonneurs et plus flexibles que les dérivés salen correspondants, capables de stabiliser des métaux à haut degré d’oxydation. Ces ligands ont également un caractère redox non-innocent, une propriété très étudiée de nos jours tant en chimie de coordination qu’en catalyse.Dans la cadre de cette thèse, différents ligands ont été synthétisés en modifiant les différents paramètres au sein du ligand : les substituants du cycle phenolate, MeO vs. tBu (PsalentBu et PsalenOMe); les substituants du phosphore, alkyl vs. aryl (iPrPsalen); et le lien entre les deux azotes, avec l’introduction de différentes o-phenylenediamines à la place d’ethylenediamine, qui donne les ligands Psalophen, PsalophenOMe2, PsalophenMe and PsalophenCF3.Les complexes neutres de cuivre et nickel, ainsi que les produits de mono-oxydation ont été synthétisés et caractérisés. Pour déterminer précisément la structure électronique des complexes différentes techniques ont été utilisés : des spectroscopies UV-visible, RMN et RPE, voltampérométrie cyclique, diffraction de rayons X, mesures magnétiques à l’état solide (SQUID), ainsi que des calculs DFT.De manière générale ces travaux montrent que les phosphasalen sont mieux à même de stabiliser la densité de spin sur le métal, donnant en certains cas des complexes à haute valence (NiIII, CuIII) encore rares dans la littérature. Dans certains cas les observations expérimentales et les calculs pointent vers un état fondamental multiconfigurationel. Contrairement aux ligands salen, les complexes portant un lien aromatique entre les deux azotes dimerisent lors de l’oxydation. Afin de contrôler la densité électronique sur ce cycle, une série des complexes à ligands phosphasalophen ont été également étudies.Une synthèse de complexes phosphasalen de manganèse(II) et (III) a été également réalisée. La stabilisation des complexes oxo ou nitrido, ainsi que la catalyse d’oxydation ont été envisagés avec ces complexes et des résultats prometteurs ont été obtenus. / Phosphasalen ligands developed in our laboratory can be considered as the phosphorous analogues of salen ligands where the imines have been substituted by iminophosphorane functions. The presence of the P-N bond makes these ligands more electro-donating and more flexible than salen analogues. They are able to stabilize high-valent metal complexes, as in the case of a Ni phosphasalen complex, which was characterized as a NiIII complex in solution and in solid state. This was never obtained before with salen-type ligands.Phosphasalen ligands, as the salen ones, can act as redox non-innocent ligands. Therefore, upon oxidation either the ligand or the metal center can be oxidized depending on the relative energy of metal and ligand orbitals. This behavior has been deeply investigated in coordination chemistry and in catalysis.In order to elucidate the factors that influence the oxidation locus different ligands have been synthetized modifiying the phenolate subtituents, MeO vs. tBu (PsalentBu and PsalenOMe); the phosphorous substituents, alkyl vs. aryl (iPrPsalen); and the linker between the two nitrogen atoms, ethylenediamine vs. phenylenediamine (Psalophen, PsalophenOMe2, PsalophenMe and PsalophenCF3).The neutral and one-electron oxidized copper and nickel complexes were synthetized and characterized. In order to determine the electronic structure of the complexes a combination of different characterization techniques were used: UV-vis, EPR and NMR spectroscopies, cyclic voltammetry, X-ray diffraction, magnetic measurements (SQUID), as well as theoretical calculations.In a general manner, phosphasalen ligands favor a metal center oxidation in a higher extent than salen derivatives, leading in some cases to high-valent metal complexes (NiIII, CuIII), remaining rare cases in the literature. For some complexes, experimental observations and theoretical calculations point to the presence of multiconfigurational ground states. Contrary to salen, complexes bearing an aromatic linker between the two nitrogen atoms dimerize upon oxidation. In order to tune the electronic density in the central ring, a series of phosphasalophen complexes displaying different substituents in the aromatic bridge, have been studied.Manganese (II) and (III) phosphasalen complexes has been also studied. The stabilization of oxo and nitride complexes as well as catalytic applications have been targeted for these complexes and encouraging results have been obtained.