Pollution from hydrofluorocarbons (HFC) poses a serious challenge to the environmental community. Released from industrial operations, they have contaminated both the atmosphere and groundwater and are considered persistent in both media.1 For over the past 20 years, the practice of synthesizing hydrofluorocarbons as alternatives to chlorofluorocarbons (CFC) has been conducted in an effort to reverse the effects of stratospheric ozone layer depletion. 2,3 However, in doing so these new fluorinated compounds exhibited an unexpected property as a potent global warming greenhouse gas (GHG) with radiative forcing potentials in the range of 100 to 10,000 equivalents greater than carbon dioxide.4 Conversely, HFCs exhibit desirable properties as precision cleaning solvents due to their low surface energy but that use has lead to releases contaminating groundwater resulting in recalcitrant pollution in the form of dense nonaqueous phase liquids (DNAPL).5 The Environmental Protection Agency (EPA) has recently requested studies on the environmental impact of HFCs with respect to a number of petitions received from various environmental action groups imploring the use of the Montreal Protocol as the vehicle by which to achieve elimination of the compounds from industrial operations.6,7 Additionally, results from studies requested by the international community have shown HFCs to exhibit developmental and neurological damage in animal life along with their impact to humans remaining not completely understood.8,9,10 Therefore, the potential hazards of HFCs to human health and the environment necessitates the development of an effective and environmentally responsible technology for their remediation from groundwater. The National Aeronautics and Space Administration (NASA) has employed the use of various halogenated solvents in its spacecraft cleaning operations at its facilities for many years iv and in that time experienced accidental releases which eventually resulted in environmental contamination.11,12,13 Many of the organic solvents employed in these operations consisted of halogenated compounds with most being partially chlorinated and fluorinated hydrocarbons. Through normal use and operation, releases of these materials found their way into the environs of atmosphere, soil and groundwater. Remediation of fluorinated compounds has not followed the successful path laid by clean-up technologies developed for their chlorinated counterparts.14,15,16,17 Fluorinated compounds are resistant however to those methods due to their unreactive nature stemming from the properties of the strong carbon-fluorine bond. 18 This unique bonding property also ensures that their environmental persistence endures. 19 One particular fluorinated groundwater contaminant, the HFC 1,1,1,2,2,3,4,5,5,5-decafluoropentane (DFP), which serves as an excellent cleaning agent and has been used by NASA since the late 1990’s and still remains in use today, was selected as the focus of this study. 20 For this study, various reductive metal systems were evaluated for their capability towards effective degradation of DFP. These included the metals: iron, magnesium, aluminum and zinc and several bimetallic alloys as well as attempts employing some on carbon support. Variations in protic solvent reaction media and acidic metal activation were also explored. The bimetallic reductive catalytic alloy, magnesium with palladium on carbon support Mg(Pd/C) in aqueous media, proved to be the successful candidate with 100% conversion to simple hydrocarbons. Mechanistic evaluation for degradation is proposed via a series of stepwise catalytic reduction reactions. Kinetic studies revealed degradation to obey second order reaction kinetics. Further study should be conducted optimizing an in situ groundwater delivery method for field application. Additionally, the developed technology should be assessed against other v groundwater fluorocarbon pollutants; either as a method for remediating multiple fluorinated polluted sites or as a polishing agent where all other non-fluorinated halogen pollutants have been abated.

No description available.

The prevalence of fluorine in natural products is scarce. There are but a handful of compounds that have been discovered to date. This could be largely attributable to the occurrence of fluorine in nature as fluoride (F-). — One might recognize such nomenclature from the ingredients list on a toothpaste tube — In fact, naturally occurring fluoride is most commonly found as fluorite (CaF2) or cryolite (Na3AlF6). As such, the introduction of fluorine via biological pathways has been limited to use of aqueous F- (a very poor nucleophile). This fact — coupled with its naturally low concentration in water — has created the ripe conditions for this shortage. In a way this has proven fertile for synthetic chemists because nature has not yet evolved a method for the deconstruction of partially or fully fluorinated compounds. Considering the above, as synthetic methodologies for the construction of carbon-fluorine bonds became available, so too did the discovery of their valuable properties. So beneficial are these properties that C-F bond-containing compounds have become commonplace in many households throughout the world. For example, practically every home relies on these compounds for use in their refrigerators. Other examples of useful fluorinated materials include blowing agents, non-stick coatings, pharmaceuticals, agrochemicals, liquid crystals, and lubricants. With all these applications and seemingly easy availability of these compounds, it is interesting to learn that original synthetic methods are still being employed today. As such, the objective of this Thesis is to develop ‘greener’ routes for the synthesis of fluorocarbons. We hypothesized that by studying transition metal-fluoroalkyl complex-mediated reactions, a more efficient catalytic system could be developed. A foreseen complication arises from the thermodynamic stability of C-F, transition metal-F and transition metal-CRF bonds. Improvements to overcome these caveats include the use of first-row late transition metal complexes. Presented herein are additions to this body of knowledge by expanding on the reactivity of nickel, copper and silver fluoroalkyl complexes. The approach applied in this work, in line with ‘green’ chemistry principles, was to source readily available fluorinated reagents, i.e. fluoroalkenes and fluoroarenes, to reduce the number of steps for the synthesis of new fluorinated compounds. Chapter 2 builds on the well-established oxidative cyclization of C2 fluoroalkenes to nickel (0), which yields new C4 units. The use of a bulky N-heterocyclic carbene ligand was found to enhance reactivity by reducing the coordination number at nickel. Examples of room temperature Cα-F and Ni-CF bond activation and functionalization reactions are presented. Chapters 3, 4 and 5 re-examine the insertion of fluoroalkenes into silver and copper fluorides and hydrides. Building on precedent of addition reactions to hexafluoropropene, this fluoroalkene was examined first. In so doing, a versatile and inexpensive copper heptafluoroisopropyl reagent was developed (Cu-F addition to (CF3)CF=CF2. With easy access to new heptafluoroisopropyl complexes, they were systemically studied for their applications in catalysis. This revealed key features, particularly the lability of the M-hfip bond, which could be detrimental to catalytic reactions. As such, a nickel complex-mediated carbonylative heptafluoroisopropylation reaction and copper complex-mediated nucleophilic addition to electrophiles were developed. When a copper hydride was used instead, the in situ generated fluoroalkyl [Cu-H addition to (CF3)CF=CF2] was susceptible to β-fluoride elimination. Chapter 4 expands this methodology to achieve the catalytic consecutive hydrodefluorination of fluoroalkenes, demonstrating the scope and limitations of this system. Furthermore, the critical role of the phosphine ligand in accessing an L3Cu-H addition and unusual β-fluoride elimination mechanism is highlighted. However, tetrafluoroethylene proved resistant to this reaction because the fluoroalkyl resting state of this alkene, Cu-CF2CF2H, is unusually robust. Chapter 5 investigates the utility of this fragment and others in C(sp2)-RF cross-coupling and nucleophilic substitutions. With focus on new routes for late stage fluorination and examples of nickel (0) complex-catalyzed selective C-F bond functionalization reactions, Chapter 5, continues studies for low-temperature and DMAP-assisted conditions for aryl-F cross-coupling reactions with boronic acid esters. Lastly, Chapter 6 reviews the advances presented in this Thesis, provides a link to the expected lasting impacts and attempts to provide guidance to future research on transition-metal complexes in the synthesis of C-F or C-RF containing compounds. Moreover, with the introduction of a new hydrodefluorination technology, previously scarce fluoroalkenes (e.g. 1,2-difluoroethylene) can now be used more freely, potentially leading to the development of new refrigerants or materials applications.

No description available.

Der Fokus dieser Dissertation lag in der Untersuchung des Potentials von Aluminium-chlorofluorid (ACF) als Katalysator für die Synthese von fluorierten Verbindungen. Insbesondere die C−F-Aktivierung von verschiedenen polyfluorierten Stoffen wurde untersucht, welches die Effizienz des festen Lewis-Säure-Katalysators für diesen Reaktionstyp zeigte. Das potente Treibhausgas 2-Chlor-1,1,1,2-tetrafluorpropan wurde erfolgreich in das dehydrofluorierte Produkt. Weiterhin wurden Umsetzungen von Pentafluorpropan-Isomeren wie z.B. 1,1,1,3,3-Pentafluorpropan, 1,1,1,2,2-Pentafluorpropan und 1,1,1,2,3-Pentafluorpropan mit ACF als Katalysator untersucht. Es konnte gezeigt werden, dass die Aktivierung der primären CH2F-Gruppe in schnell stattfindet und dabei keine Wasserstoffquelle erfordert. Im Kontrast dazu, wurde für die Aktivierung von CF2-Gruppen eine Wasserstoffquelle wie etwa HSiEt3 benötigt und resultierte in der Bildung eines Produktgemischs. Alternativ wurden Hydrofluorierungsreaktionen von mehreren Substraten durch die Synthese und den Einsatz eines neuen Materials erreicht, welches auf der Immobilisierung von HF auf der Oberfläche von ACF beruht. Dieses HF-ACF wurde unter der Verwendung von vielfältigen Charakterisierungsmethoden umfassend untersucht. Die innere Struktur des Festkörpers, wurden mit MAS-NMR-Spektroskopie, FTIR, Inelastische Neutronenstreuung, XRD und Thermoanalyse analysiert Dadurch konnte gezeigt werden, dass eine geringfügige Reorganisation des bulks zu einer besser geordneten Matrix und die Bildung einer mit der ACF-Oberfläche wechselwirkenden Polyfluorid-Struktur vorliegt. Zur Bestimmung der Oberflächengröße wurde das BET-Modell genutzt und zur Analyse der Porengröße wurde die NLDFT verwendet. Abschließend wurden verschiedene Probeverbindungen an der Oberfläche des HF-ACFs adsorbiert um die Azidität der Oberfläche zu bestimmen und es konnte gezeigt werden, dass eine signifikante Reduktion der Lewis- und Brønsted-Azidität vorliegt. / The main focus of this thesis lies in the study of the potential of aluminum chlorofluoride (ACF) as a catalyst for the synthesis of fluorinated compounds. In particular, C−F bond activations of various polyfluorinated compounds were studied, showing the efficiency of this solid Lewis acid catalyst for this type of reaction. The potent greenhouse gas 2-chloro-1,1,1,2-tetrafluoropropane was successfully transformed into the dehydrofluorination product 2-chloro-3,3,3-trifluoropropene under mild conditions. Similarly, transformation of pentafluoropropane isomers, such as 1,1,1,3,3-pentafluoropropane, 1,1,1,2,2- pentafluoropropane and 1,1,1,2,3-pentafluoropropane was also investigated using ACF as a catalyst. It was evidenced that the primary CH2F group present in 1,1,1,2,3-pentafluoropropane was easily activated without the need for a hydrogen source. In contrast, to activate CF2 groups, a hydrogen source such as HSiEt3 was required, generating a variety of products. Alternatively, successful hydrofluorination reactions of several substrates were conducted by synthesizing a new material, based on the loading of hydrogen fluoride (HF) at the surface of ACF. This HF-loaded ACF was deeply studied using a wide range of characterization methods. For the bulk, MAS NMR spectroscopy, Fourier Transform Infrared spectroscopy (FTIR), Inelastic Neutron Scattering (INS), Powder X-Ray Diffraction (P-XRD), and thermoanalysis were performed, revealing a slight reorganization of the bulk towards a better-ordered matrix and the formation of polyfluoride structure interacting with the surface of ACF. The BET model was used for the surface area determination, and the pore size analysis was established using the non local density functional theory (NLDFT). Finally, various probe molecules were adsorbed at the surface of HF-loaded ACF to determine the acidity of the surface, revealing a significantly reduced Lewis and Brønsted acidity.