Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

In this thesis, the synthesis and reactivity of metal complexes containing phosphido (PR2−) and phosphenium (PR2+) ligands for the hydrophosphination of alkenes were investigated. The mechanisms of hydrophosphination mediated by these M-PR2 fragments were explored. Based on previous work in the Rosenberg group, Ru(η5-indenyl) complexes were explored and developed as catalysts for hydrophosphination. It was determined that Ru-phosphido complexes are key intermediates in the hydrophosphination of electron-deficient alkenes. A detailed study on the mechanisms of hydrophosphination catalyzed by the phosphido complexes Ru(η5-indenyl)(PPh2)(L)(PPh3) (4a, L = NCPh; b, L = PPh2H; c, L = CO) was performed. Evidence for product inhibition was found for this catalyst system using Reaction Progress Kinetic Analysis. Product inhibition is consistent with the observed catalyst resting state of a complex containing product phosphines and the determination that substitution of the product phosphine from Ru is rate-limiting. The ancillary ligands (L) of 4 were found to influence catalytic activity by enabling catalyst deactivation (L = NCPh) or off-cycle processes including alkene telomerization (L = CO). Proposed mechanisms for catalysis were devised based on these findings. These results are important mechanistic insights that will be useful for designing new catalysts for hydrophosphination. The unprecedented viability of metal phosphenium complexes as intermediates in hydrophosphination was also explored. Three Mo phosphenium complexes were synthesized via P-H bond hydride abstraction from coordinated secondary phosphines, PR2H. These complexes were found to mediate the stoichiometric hydrophosphination of alkenes and ketones. In particular, trans-[Mo(CO)3(PPh2H)2(PPh2)]+ (13) mediates the hydrophosphination of a wide scope of alkenes that includes ethylene, propene and 1-hexene, which are challenging substrates for metal-catalyzed hydrophosphination. Preliminary attempts were conducted to render this synthetic phosphenium-mediated hydrophosphination catalytic. These results provide evidence for the putative steps of a hydrophosphination cycle utilizing metal phosphenium complexes as intermediates. The phosphenium complexes trans-[Mo(CO)4(PR2H)(PR2)] (12a R = Tolp2, b R = Ph) were also investigated as Lewis acid catalysts for hydrosilylation. A tentatively-assigned η1-HSiEt3 adduct of 12a, [Mo(CO)4(PTolp2H)(PTolp2{HSiEt3})] (20a), was observed by low temperature 31P{1H} NMR and was studied computationally. Complex 12b is proposed to behave as a Lewis acid catalyst for hydrosilylation. An off-cycle equilibrium is proposed that results in the formation of EtSi+. This work is a unique example of P(III) Lewis acid catalysis, of which there are few examples in the literature. / Graduate / 2020-07-29

In chapter 1, I discuss how ligand architecture in tripodal nitrogen-rich ligands can drastically affect the structure of zinc complexes featuring these ligands. The synthesis and characterization of zinc tris(1-methylimidazol-2-ylthio)methyl ([Titm^Me]) and tris(1-Pribenzimidazol-2-ylthio)methyl ([Titm^iPr,benzo]) complexes is presented. The ligand in [Titm^Me]Zn complexes binds the metal to form carbatrane structures that exhibit unusually long and flexible Zn–C bonds. The bonding between the zinc and the carbon in these complexes can therefore be more accurately described as a zwitterionic interaction between a carbanion and a zinc cation. Density functional theory calculations demonstrate that the energy profile for the Zn–C bond is shallow, such that large variations of the Zn–C distance result in very little change in the energy of the complex. The benzannulated ligand [Titm^iPr,benzo] allows access to a rare monomeric zinc hydride species [κ³-Titm^iPr,benzo]ZnH that can react with either CO₂ to produce a zinc formate, or B(C₆F₅)₃ to form the ion pair [κ⁴-Titm^iPr,benzo]ZnHB(C₆F₅)₃. The coordination chemistry of the [Titm^iPr,benzo] ligand also extends to the other metals of group 12. In chapter 2, I report the use of the [Titm^Me] and [Titm^iPr,benzo] zinc complexes presented in chapter 1 as biomimetic models for zinc enzymes. First, [Titm^Me] zinc complexes present structural similarities with the active site of carbonic anhydrase, and can be used to study the binding of carbonic anhydrase inhibitors to the enzyme active site. Then, [κ⁴-Titm^iPr,benzo]ZnX (X = MeB(C₆F₅)₃, BPh₄) complexes and their interactions with ligands of relevance towards antibiotic resistance is reported. The non coordinating nature of the anions in [κ⁴-Titm^iPr,benzo]ZnX (X = MeB(C₆F₅)₃, BPh₄) lead to the formation of a Lewis acidic zinc cationic center, which can be coordinated by an additional ligand of biological interest. The binding of simple β-lactams to the [κ⁴-Titm^iPr,benzo]ZnX complexes can be probed using X-ray diffraction and Nuclear Magnetic Resonance (NMR) spectroscopy, thereby providing a way to model the binding of antibiotics to the active site of the metallo-β-lactamases enzymes responsible for broad antibiotic resistance. The binding of β-lactams can be compared to larger ring size lactams and linear amides. [κ⁴-Titm^iPr,benzo]ZnX (X = MeB(C₆F₅)₃, BPh₄) also allows for the study of the binding of potential metallo-β-lactamases inhibitors, such as, for example, glycinamide, picolinamide, and piperazine-2,3-dione. Binding studies between [κ⁴-Titm^iPr,benzo]ZnX and substrates bearing structural similarities to antibiotics reveal secondary interactions involving peripheral functional groups the cationic zinc center in [κ⁴-Titm^iPr,benzo]ZnX. These studies provide guidelines to modify existing antibiotics, in order to decrease their sensitivity to metallo-β-lactamases. In chapter 3, I explore the reactivity of previously characterized tris(2-pyridylthio)methyl [Tptm] zinc complexes. First, an improved synthesis of [κ⁴-Tptm]ZnF using Me₃SnF as the fluorinating agent is reported. The fluorine atom in [κ⁴-Tptm]ZnF acts as a Lewis base, as illustrated by its reaction with B(C₆F₅)₃ to form [κ⁴-Tptm]ZnFB(C₆F₅)₃, in which the fluorine is transferred to the borane group. The fluoride ligand in [κ⁴-Tptm]ZnF also acts as a hydrogen bond and halogen bond acceptor and is capable of forming adducts with H₂O, indole, and iodopentafluorobenzene. [κ⁴-Tptm]ZnF undergoes metathesis with Ph₃CCl to form Ph₃CF, thereby providing a rare example of C–F bond formation promoted by a zinc complex. Then, [κ³-Tptm]ZnH is used as a catalyst for the hydrosilylation of aldehydes and ketones using phenylsilane to produce tris alkoxysilane products. The catalyst is very active with aldehydes, and shows slower reactivity towards dialkyl ketones. The reaction proceeds via insertion of the carbonyl group in the Zn–H bond to form a zinc alkoxide, which then undergoes metathesis with the silane to generate the desired product and regenerate the zinc hydride species. The complicated NMR spectroscopic features of the products resulting from the hydrosilylation of prochiral ketones are explained by the presence of different diastereomers. Finally, we report that [κ³-Tptm]ZnH is a catalyst for the hydrosilylation of silylformates to methoxy silanes with (EtO)₃SiH, (MeO)₃SiH and κ⁴-N(CH₂CH₂O)₃SiOMe. We show that CO₂ can be reduced to methoxy silane species in a one pot reaction using (MeO)₃SiH and catalytic amounts of [κ³-Tptm]ZnH. In chapter 4, I report the synthesis and characterization of a silicon based analogue of [Titm^iPr,benzo], namely the tris(1-Pribenzimidazol-2-yldimethylsilyl)methyl [Tism^iPr,benzo] ligand. The ligand possesses unique structural features, due to the proximity between the dimethylsilyl groups and the methyl carbanion. The formation of [κ⁴-Tism^iPr,benzo]Li proceeds via the doubly base stabilized silene intermediate [κ³-C(SiMe₂benzimid^iPr)₂]SiMe₂. [κ⁴-Tism^iPr,benzo]Li can be used as a precursor for copper and nickel [Tism^iPr,benzo] and [C₃-Tism^iPr,benzo] complexes, where [C3-Tism^iPr,benzo] represents the isomerized tris carbene version of [Tism^iPr,benzo]. [κ³-C(SiMe₂benzimid^iPr)₂]SiMe₂ reacts with ZnMe₂ to produce [κ³-C(SiMe₃)(SiMe₂benzimid^iPr)₂]ZnMe, which can be transformed to the phenoxide compound. This compound acts as a catalyst for the hydrosilylation of CO₂ to silyl formates and methoxy silanes. [κ³-C(SiMe₂benzimid^iPr)₂]SiMe₂ itself reacts with CO₂ to produce an unusual β-lactone.

Thèse doctorat : Matériaux Polymères & Composites : Villeurbanne, INSA : 2003. / Titre provenant de l'écran-titre. Bibliogr. p. 223-238.

The thesis presents the research results obtained while studying novel chemical strategies for preparing Si(100)-based electrochemical platforms suitable for aqueous environments. A primary research aim was the preparation of well-passivated Si(100) surfaces amenable to further chemical derivatization. The preparation and functionalization of alkyne-terminated alkyl monolayers on Si(100) surfaces using the Huisgen 1,3-dipolar ???click??? cycloaddition of azides with surface-bound acetylenes is reported and shown to be a versatile, experimentally simple, chemically unambiguous modular approach to modified silicon surfaces. Covalently immobilized, structurally well-defined acetylenyl organic monolayers are prepared from a commercially available ??,??-diyne (1,8-nonadiyne) species using a one-step thermal hydrosilylation procedure. Subsequent derivatization of the alkyne-terminated monolayers in aqueous environments with representative azide species affords disubstituted surface-bound [1,2,3]-triazole species. Neither activation procedures nor protection/deprotection schemes are required, as is the case with more established grafting approaches for silicon surfaces. The described surface modification scheme has been used in preparing modified Si(100) electrode surfaces, where modular components such as ferrocene derivatives or electrochemically ???switchable??? linker molecules are introduced onto the passivated silicon surface. An implementation study to prepare modified light-addressable ???switchable??? Si(100) electrodes is also reported. Negligible oxidation of the substrate was generally observed after exposure to aqueous systems for extended periods (tens of hours), and the electroactive monolayers showed a robust and reversible behaviour. The proposed concept of modular components and high-yielding coupling procedures has been shown on Si(100) surfaces and also extended to illustrate the functionalization of porous silicon rugate filters.

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