This dissertation focuses on the development of cyclopentadienes as an emerging class of compounds for use in catalysis. Previous work in the Lambert group had established pentacarboxycyclopentadienes (PCCPs) as a promising class of Brønsted acids capable of being used as catalysts in acid-promoted reactions. The ease of their synthesis distinguished them from the comparable BINOL-derived phosphoric acids, and their unique mode of enantioinduction created opportunities for their use in enantioselective reactions. Initial efforts were focused on the synthesis of leading to the development of two complementary methods for their synthesis. Chapter 2 details the improvements made to the transesterification of penta(methoxycarbonyl)cyclopentadiene, which allowed for sterically encumbered alcohols to be used. Further, a new method for accessing the penta-acyl chloride intermediate was developed, leading to the ability for a wide array of electron-deficient PCCPs to be synthesized. The second half of the dissertation examines the use of electrophilic silicon reagents and their use as Lewis acids. Given our ability to access highly electron-deficient cyclopentadienes, the silyl cyclopentadienes were targeted as potential Lewis acids. Chapter 4 details the synthesis of these species, and their characterization. Having established a convenient route to silyl mono(carboxy)tetracyanocyclopentadienides, we examined their use as catalysts in halide abstraction reactions. Benzylic bromides could be activated and subsequently allylated, or arylated with a nucleophilic arene using allyltrimethylsilane as a sacrificial silyl source.

Persistent organic pollutants are a well-known threat to the environment. Substances such as polycyclic aromatic hydrocarbons and chlorinated organic compounds in contaminated soil and groundwater can have severe and long-lasting effects on health in animals and humans. There is an urgent need for the development of safe technologies for their effective removal. Originally developed for mineral processing, mechanical treatment by ball milling is an extremely versatile technique for the degradation of toxic compounds. Reactive milling can rapidly destroy organic compounds without producing hazardous wastes. Complete breakdown of the organic molecules is achieved after relatively short milling times. Successful tests were conducted on polychlorobiphenyls (PCBs), DDT, DDD, DDE, Dieldrin and hexachlorobenzene with a conversion yield in the of greater than 99% (Hall et al., 1996; Monagheddu et al., 2000; Zhang et al., 2001; Zhang et al., 2002; Tanaka and Zhang, 2003; Pizzigallo et al., 2004; Nomura et al., 2005; Bellingham, 2006).In this study reactive ball milling was used to investigate the destruction of two classes of persistent organic pollutants environmental contaminants. The compounds studied are either known environmental pollutants or simple analogues. These were chosen as being representative of pollutants to investigate the pathway using ball milling destruction and in most cases were relatively small molecules so that the intermediates could be more easily identified. The first class of compounds was polycyclic aromatic compounds. Some smaller members of this class such as naphthalene, anthracene were investigated. The second class of compounds were some analogues of environmentally hazardous hydroxylated and halogenated compounds such as chloronaphthalene, bromonaphthalene, 1- naphthol, 2-naphthol and pentachlorophenol under reactive milling using GCMS analysis of the degradation pathway. Destruction efficiencies greater than 99% have been achieved for a number of organic compounds. Several different intermediates have been identified during the milling degradation. There was also some evidence from this study that halogens could be transferred between compounds during milling. The final products of the milling destruction of these compounds are an amorphous carbon residue and inorganic chloride or bromides. It was proposed that large amounts of halogens could be found however the results showed that small amounts detected. At early stages of milling a number of intermediate breakdown products were detected which were destroyed on extended milling. The core objective of this research was to clarify the reaction mechanisms pathways used of more complex polycyclic aromatic hydrocarbons and aromatic organ halogen compounds. This study is a part of a long-term research project on the destruction of toxic organic compounds by reactive milling.

Persistent organic pollutants are a well-known threat to the environment. Substances such as polycyclic aromatic hydrocarbons and chlorinated organic compounds in contaminated soil and groundwater can have severe and long-lasting effects on health in animals and humans. There is an urgent need for the development of safe technologies for their effective removal. Originally developed for mineral processing, mechanical treatment by ball milling is an extremely versatile technique for the degradation of toxic compounds. Reactive milling can rapidly destroy organic compounds without producing hazardous wastes. Complete breakdown of the organic molecules is achieved after relatively short milling times. Successful tests were conducted on polychlorobiphenyls (PCBs), DDT, DDD, DDE, Dieldrin and hexachlorobenzene with a conversion yield in the of greater than 99% (Hall et al., 1996; Monagheddu et al., 2000; Zhang et al., 2001; Zhang et al., 2002; Tanaka and Zhang, 2003; Pizzigallo et al., 2004; Nomura et al., 2005; Bellingham, 2006).In this study reactive ball milling was used to investigate the destruction of two classes of persistent organic pollutants environmental contaminants. The compounds studied are either known environmental pollutants or simple analogues. These were chosen as being representative of pollutants to investigate the pathway using ball milling destruction and in most cases were relatively small molecules so that the intermediates could be more easily identified. The first class of compounds was polycyclic aromatic compounds. Some smaller members of this class such as naphthalene, anthracene were investigated. The second class of compounds were some analogues of environmentally hazardous hydroxylated and halogenated compounds such as chloronaphthalene, bromonaphthalene, 1- naphthol, 2-naphthol and pentachlorophenol under reactive milling using GCMS analysis of the degradation pathway. Destruction efficiencies greater than 99% have been achieved for a number of organic compounds. Several different intermediates have been identified during the milling degradation. There was also some evidence from this study that halogens could be transferred between compounds during milling. The final products of the milling destruction of these compounds are an amorphous carbon residue and inorganic chloride or bromides. It was proposed that large amounts of halogens could be found however the results showed that small amounts detected. At early stages of milling a number of intermediate breakdown products were detected which were destroyed on extended milling. The core objective of this research was to clarify the reaction mechanisms pathways used of more complex polycyclic aromatic hydrocarbons and aromatic organ halogen compounds. This study is a part of a long-term research project on the destruction of toxic organic compounds by reactive milling.

Este trabalho teve como objetivo avaliar a sensibilidade da formação do ozônio troposférico às emissões veiculares de compostos orgânicos voláteis (COVs) e NOx na Região Metropolitana de São Paulo (RMSP). Essa avaliação foi realizada através de modelagem numérica com modelo de qualidade do ar fotoquímico tridimensional. Para a determinação da especiação dos COVs veiculares foram realizadas duas campanhas intensivas de medidas em túneis da cidade de São Paulo, constituindo portanto em um esforço na melhoria do inventário de emissões da RMSP. Das medidas de concentração dos COVs, CO, NOx e SO2 foram calculados fatores de emissão e com base na relação entre as concentrações dos COVs emitidos pela exaustão veicular, juntamente com informações obtidas previamente da composição do combustível líquido e das emissões evaporativas foi construído um inventário dos COVs emitidos pela gasolina, álcool e diesel na RMSP, utilizado nas simulações de qualidade do ar. Foram realizadas simulações de referência utilizando o modelo fotoquímico densenvolvido no Caltech Institute of Technology (CIT) e Carnegie Mellon University, e as concentrações obtidas das simulações foram comparadas às concentrações observadas pela rede de monitoramento da Companhia de Tecnologia de Saneamento Ambiental (CETESB) para três períodos distintos, em termos dos níveis de poluição e condições meteorológicas: 22-24 de agosto de 2000; 13-15 de março de 2000 e 06-10 de setembro de 2004. Com base nas simulações de referência foram calculados os potenciais de formação de ozônio para 24 espécies através do cálculo de métricas de reatividade e também realizada a análise da sensibilidade da formação do ozônio às emissões de COVs, NOx, CO e de cada COV individualmente para os três períodos. Da avaliação da análise de sensibilidade do ozônio às emissões pôde-se verificar que o ozônio foi altamente sensível às emissões dos COVs nos três períodos estudados e portanto, o controle da emissão dos COVs é o mais efetivo para o controle do ozônio na RMSP. Dentre os COVs analisados as espécies representadas por ARO2 (aromáticos 2), OLE1 (olefinas 1), OLE2 (olefinas 2), ETHE (eteno) e HCHO (formaldeído) foram as cinco às quais o ozônio (medido em termos de seu potencial de formação e emissão) apresentou maior sensibilidade constituindo-se nas mais relevantes. Adicionalmente, foram avaliados os impactos de diferentes cenários de uso de gasolinas reformuladas nas concentrações de ozônio em todo o domínio em relação ao cenário atual de referência. A máxima resposta do ozônio às reduções de emissão foi obtida após 3 dias do início do controle. Os cenários 1 (redução de 11,1% das frações de olefinas, aromáticos e benzeno da gasolina) e 2 (redução de 20,0% das frações de olefinas, aromáticos e benzeno da gasolina) que refletem as propostas de reformulação da gasolina para 2007 e 2009 resultaram em reduções das concentrações de ozônio, mas insuficientes para a redução para abaixo do padrão de qualidade do ar de ozônio. / The main goal of this work was the study of the ozone sensitivity to volatile organic compounds (VOCs) and NOx emitted by vehicles in the Metropolitan Area of São Paulo (MASP), using as tool the numerical modeling. Two intensive campaigns in-tunnel of São Paulo city were performed as an effort to improve the MASP emission inventory. From concentrations measurements of VOCs, CO, NOx and SO2 they were calculated emission factors and based on the relation among the VOCs emitted by exhaust, and also together with informations from liquid fuel and evaporative composition was built the VOCs composition from gasoline, alcohol and diesel emission in the MASP. Together with the totals emitted officially, it was obtained the inventory of emissions used in the simulation. Base case simulations were performed using the photochemical model developed at Caltech Institute of Technology (CIT) and Carnegie Mellon University, and the concentrations simulated were compared with observations from the air quality network of the São Paulo State Companhia de Tecnologia de Saneamento Ambiental (CETESB). Three periods were studied: August 22-24 of 2000; March 13-15 of 2000 and September 06-10 of 2004. Ozone potential formation was calculated for 24 species using reactivity metrics, and was also performed the ozone sensitivity analysis to emission of VOCs, NOx, CO and each VOC individually, for all the periods. From ozone sensitivity analysis to emissions, it was found that the ozone is higher sensitivity to VOCs emissions than to NOx. Therefore, the VOCs reduction is more effective on ozone control in the MASP. Among the VOCs analyzed the species represented by ARO2 (aromatics 2), OLE1 (olefins 1), OLE2 (olefins 2), ETHE (ethene) and HCHO (formaldehyde) were identified as the most important concerning ozone formation in the MASP. Additionally, the impacts of different scenarios of reformulated gasoline in the ozone concentrations in whole domain and time were evaluated in relation to current scenario (base case). The higher reductions of ozone associated to emission control was identified to occur after 3 days of the beginning of control. The scenarios 1 (reduction of 11.1% of the olefins, aromatics and benzene fractions from gasoline) and 2 (reduction of 20.0% of the olefins, aromatics and benzene fractions from gasoline) that reflect the proposals for reformulated gasoline in 2007 and 2009 resulted in reductions of the ozone concentrations, but insufficient for the reduction below of the ozone air quality standard.

Este trabalho teve como objetivo avaliar a sensibilidade da formação do ozônio troposférico às emissões veiculares de compostos orgânicos voláteis (COVs) e NOx na Região Metropolitana de São Paulo (RMSP). Essa avaliação foi realizada através de modelagem numérica com modelo de qualidade do ar fotoquímico tridimensional. Para a determinação da especiação dos COVs veiculares foram realizadas duas campanhas intensivas de medidas em túneis da cidade de São Paulo, constituindo portanto em um esforço na melhoria do inventário de emissões da RMSP. Das medidas de concentração dos COVs, CO, NOx e SO2 foram calculados fatores de emissão e com base na relação entre as concentrações dos COVs emitidos pela exaustão veicular, juntamente com informações obtidas previamente da composição do combustível líquido e das emissões evaporativas foi construído um inventário dos COVs emitidos pela gasolina, álcool e diesel na RMSP, utilizado nas simulações de qualidade do ar. Foram realizadas simulações de referência utilizando o modelo fotoquímico densenvolvido no Caltech Institute of Technology (CIT) e Carnegie Mellon University, e as concentrações obtidas das simulações foram comparadas às concentrações observadas pela rede de monitoramento da Companhia de Tecnologia de Saneamento Ambiental (CETESB) para três períodos distintos, em termos dos níveis de poluição e condições meteorológicas: 22-24 de agosto de 2000; 13-15 de março de 2000 e 06-10 de setembro de 2004. Com base nas simulações de referência foram calculados os potenciais de formação de ozônio para 24 espécies através do cálculo de métricas de reatividade e também realizada a análise da sensibilidade da formação do ozônio às emissões de COVs, NOx, CO e de cada COV individualmente para os três períodos. Da avaliação da análise de sensibilidade do ozônio às emissões pôde-se verificar que o ozônio foi altamente sensível às emissões dos COVs nos três períodos estudados e portanto, o controle da emissão dos COVs é o mais efetivo para o controle do ozônio na RMSP. Dentre os COVs analisados as espécies representadas por ARO2 (aromáticos 2), OLE1 (olefinas 1), OLE2 (olefinas 2), ETHE (eteno) e HCHO (formaldeído) foram as cinco às quais o ozônio (medido em termos de seu potencial de formação e emissão) apresentou maior sensibilidade constituindo-se nas mais relevantes. Adicionalmente, foram avaliados os impactos de diferentes cenários de uso de gasolinas reformuladas nas concentrações de ozônio em todo o domínio em relação ao cenário atual de referência. A máxima resposta do ozônio às reduções de emissão foi obtida após 3 dias do início do controle. Os cenários 1 (redução de 11,1% das frações de olefinas, aromáticos e benzeno da gasolina) e 2 (redução de 20,0% das frações de olefinas, aromáticos e benzeno da gasolina) que refletem as propostas de reformulação da gasolina para 2007 e 2009 resultaram em reduções das concentrações de ozônio, mas insuficientes para a redução para abaixo do padrão de qualidade do ar de ozônio. / The main goal of this work was the study of the ozone sensitivity to volatile organic compounds (VOCs) and NOx emitted by vehicles in the Metropolitan Area of São Paulo (MASP), using as tool the numerical modeling. Two intensive campaigns in-tunnel of São Paulo city were performed as an effort to improve the MASP emission inventory. From concentrations measurements of VOCs, CO, NOx and SO2 they were calculated emission factors and based on the relation among the VOCs emitted by exhaust, and also together with informations from liquid fuel and evaporative composition was built the VOCs composition from gasoline, alcohol and diesel emission in the MASP. Together with the totals emitted officially, it was obtained the inventory of emissions used in the simulation. Base case simulations were performed using the photochemical model developed at Caltech Institute of Technology (CIT) and Carnegie Mellon University, and the concentrations simulated were compared with observations from the air quality network of the São Paulo State Companhia de Tecnologia de Saneamento Ambiental (CETESB). Three periods were studied: August 22-24 of 2000; March 13-15 of 2000 and September 06-10 of 2004. Ozone potential formation was calculated for 24 species using reactivity metrics, and was also performed the ozone sensitivity analysis to emission of VOCs, NOx, CO and each VOC individually, for all the periods. From ozone sensitivity analysis to emissions, it was found that the ozone is higher sensitivity to VOCs emissions than to NOx. Therefore, the VOCs reduction is more effective on ozone control in the MASP. Among the VOCs analyzed the species represented by ARO2 (aromatics 2), OLE1 (olefins 1), OLE2 (olefins 2), ETHE (ethene) and HCHO (formaldehyde) were identified as the most important concerning ozone formation in the MASP. Additionally, the impacts of different scenarios of reformulated gasoline in the ozone concentrations in whole domain and time were evaluated in relation to current scenario (base case). The higher reductions of ozone associated to emission control was identified to occur after 3 days of the beginning of control. The scenarios 1 (reduction of 11.1% of the olefins, aromatics and benzene fractions from gasoline) and 2 (reduction of 20.0% of the olefins, aromatics and benzene fractions from gasoline) that reflect the proposals for reformulated gasoline in 2007 and 2009 resulted in reductions of the ozone concentrations, but insufficient for the reduction below of the ozone air quality standard.