As moléculas à base de nitrogênio, NH2Ph, NH2CH2Ph e NHnBuPh foram investigadas como ligantes ancilares nos novos complexos do tipo [RuCl2 (PPh3)2 (amina) x] para a polimerização via metátese por abertura de anel (ROMP) de norborneno (NBE), norbornadieno (NBD) e diciclopentadieno (DCPD). Os complexos foram obtidos da síntese com [RuCl2 (PPh3)3] com as respectivas moléculas. E eles foram caracterizados por análise elementar de CHN, FT-IR, RMN 31P{1H}, Espectroscopia eletrônica na região do uv-vis e voltametria cíclica. Os complexos isolados foram hexacoordenados (x = 2) com NH2Ph e NH2CH2Ph, e pentacoordenado com NHnBuPh (x = 1). Além disso, os resultados sugerem que todos os ligantes estão trans-posicionados no caso do complexo com NH2Ph (complex 1) e cis no caso do complexo com NH2CH2Ph (complex 2). O complexo com NHnBuPh ( complex 3) e sugerido estar na geometria pirâmide de base quadrada, com a amina no eixo axial. Quantitativos rendimentos foram obtidos na ROMP de NBE a 50°C com 1 por 30 min e com 2 por 5 minutos. Similar resultado foi obtido com 3 at 25°C por 5 min. O valor de Mw foram na faixa de 104 e 105 g/mol,com valores de IPD entre 1,6 e 3,5. Os valores de σc foram em torno de 0,40 a 0,52. ROMP de NBE e DCPD, bem como copolimerizações foram também realizadas com melhores resultados com 3. Os resultados são discutidos em termos de densidade eletrônica e impedimento estérico das aminas como ligantes ancilares nos complexos. As reações com o complexo 2 são favoráveis pelo caráter σ-doador, enquanto que o grande ângulo de cone da NHnBuPh prove a reatividade de 3. / The nitrogen-based molecules, NH2Ph, NH2CH2Ph and NHnBuPh were investigated as ancillary ligands in the new [RuCl2 (PPh3)2 (amine) x] complex types for Ring Opening Metathesis Polymerization (ROMP) of norbornene (NBE), norbornadiene (NBD) and dicyclopentadiene (DCPD). The complexes were obtained from syntheses with [RuCl2 (PPh3)3]of and the respectively molecules and they were characterized by elementar analysis of CHN, FT-IR, NMR 31P, uv-vis spectroscopy and cyclic voltammetry. The isolated complexes were sixcoordinated (x = 2) with NH2Ph and NH2CH2Ph and pentacoordinated with NHnBuPh (x = 1). Moreover, the data suggest that all the ligands are trans-positioned in the case of NH2Ph (complex 1) and cis-positioned in the case of NH2CH2Ph (complex 2). The complex with NHnBuPh (3) was suggested to present a square pyramidal geometry with the amine in the axial axis. Quantitative yields were obtained in the ROMP of NBE at 50 °C with 1 for 30 min and with 2 for 5 min. Similar result was obtained with 3 at 25 °C for 5 min. The Mw values were in the range of 104 to 105 g/mol with PDI values between 1.6 and 3.5. The σc values were 0.40 to 0.52. ROMP of NBD and DCPD, as well copolymerizations with NBE, NBD and DCPD, were also performed with better results with 3. The results are discussed in terms of the electronic density and steric hindrance from the amines as ancillary ligands in the complexes. The reactions with complex 2 are favored by the σ-donor character of NH2CH2Ph, whereas the large cone angle of NHnBuPh provided the reactivity with 3.

A influência da isomeria cis/trans na reatividade de complexos do tipo [RuCl2(DMSO)3(L)], onde L = DMSO (2;4), n-butilamina (1;3) na polimerização via metátese por abertura de anel (ROMP) foi investigada. Os complexos 1 e 2 apresentaram isomeria fac, enquanto que os complexos 3 e 4 foram trans e mer, respectivamente. Os dados cristalográficos sugerem uma conformação fac para o novo complexo 1. Os parâmetros eletrônicos e estéreos dos ligantes, medidos pelos valores de pka e θ, respectivamente, foram usados para interpretação dos resultados. Os monômeros cíclicos usados foram norborneno (NBE), norbornadieno (NBD) e diciclopentadieno (DCPD), considerando como parâmetros as razões molares monômero/complexo, temperatura, tempo de reação e estrutura geométrica. Complexos cis foram mais ativos do que os complexos trans para a polimerização de norborneno e de norbornadieno, sendo os resultados a 50 oC melhores do que os resultados a 25 oC. Na polimerização de norbornadieno, ao contrário da polimerização com norborneno, os melhores rendimentos foram obtidos com os complexos contendo os ligantes cloro trans-posicionados. Os compostos isolados foram caracterizados por analise elementar, FTIR, voltametria cíclica, espectroscopia na região do UV-vis, RMN de 1H e 13C e espectroscopia de difração de raio-x. Em adição, combinação de resultados teóricos e dados experimentais para a reação de ROMP de norborneno usando [RuCl2(PPh3)2(piperidina)] mostra a otimização estrutural das espécies envolvidas na catálise e o perfil termodinâmico de toda reação. Fatores entrópicos explicam a espontaneidade observada para a dissociação de grupos de saída, que são processos endotérmicos. Logo após a etapa determinante da velocidade, ocorre a coordenação de uma molécula de norborneno e um efeito trans-sinérgico entre este monômero e o ligante piperidina ativa a catálise. O uso de outros diazocompostos (TBDA e BDA) foi feito para analisar as influências eletrônicas e estéricas do carbeno em questão. Efeitos eletrônicos tem menos influência sobre a estrutura da espécie ativa do que os efeitos estéricos, influenciando nos rendimentos e nos dados dos polímeros formado. / The influence of cis/trans isomery on the reactivity of complexes of the type [RuCl2(DMSO)3(L)], where L = DMSO (2;4), n-butylamine (1;3) in the ring-opening metathesis polymerization (ROMP) was investigated. The complexes 1 and 2 showed isomerism fac, while the complexes were 3 and 4 were trans and mer, respectively. The crystallographic data suggest a fac conformation for the new complex 1. The electronic and steric parameters from ligands, measured by pKa values and θ, respectively, were used for interpretation of the results. The cyclic monomers used were norbornene (NBE), norbornadiene (NBD) and dicyclopentadiene (DCPD), given as parameters the molar ratios monomer/complex, temperature, reaction time and geometric structure. The cis complexes were more active than the trans complex for polymerization of norbornene and norbornadiene, and the results at 50 oC better than the results at 25 oC. The polymerization of norbornadiene, unlike the polymerization of norbornene, best yields were obtained with complexes containing trans-positioned chloro ligands. All compounds were characterized by elemental analysis, FTIR, cyclic voltammetry, UV-vis spectroscopy, NMR 1H and 13C spectroscopy and x-ray diffraction. In addition, combination of theoretical and experimental results data for ROMP reactions of norbornene using [RuCl2(PPh3)2(piperidine)] shows the structural optimization of the species involved in the catalysis and the thermodynamic profile of the whole reaction. Entropic factors explain the spontaneity observed for dissociation from both leaving groups, which are endothermic processes. Immediately after the rate-determining step occurs the coordination of a norbornene molecule and a trans- synergistic effect between the monomer and ligand piperidine actives the catalysis. The use of other diazocompostos (TBDA and BDA) was done to analyze the electronic and steric influences of the carbene in question. Electronic effects had less influence on the structure of the active species than the steric effects, influencing the yield and the data of the polymers formed.

Polímeros com diferentes características foram sintetizados a partir da polimerização por abertura de anel (Ring Opening Metahesis Polymerization-ROMP) de três diferentes monômeros de norborneno (NBE) derivados com triglicerídeos ou monoglicerídeos oriundos de óleos de mamona e de soja: Norbornenyl-functionalized castor oil (NCO), Norbornenyl-functionalized castor oil alcohol (NCA) e o novo Norbornenyl-functionalized epoxized soybean oil (NESBO). Utilizou-se como precursores catalíticos complexos do tipo [RuCl2(PPh3)2(amina)], amina = peridroazepina e piperidina, e catalisadores de Grubbs (1a e 2a geração). Foram investigados os efeitos da estrutura do monômero e do catalisador no processo de polimerização, bem como as propriedades térmicas e mecânicas dos polímeros resultantes. Através da ressonância magnética nuclear de hidrogênio (NMR-1H) foi determinado o número de sítios ativos (unidades de norborneno) por cadeia de ácido graxo em cada monômero: 1,8 em NCO, 2,6 em NCA e 4.5 em NESBO. O número de unidades monoméricas, assim como a viscosidade de cada monômero, desempenha um papel importante no controle da iniciação e propagação do processo de polimerização e nas propriedades finais dos polímeros obtidos. Os complexos do tipo Ru-amina, produziram materiais poliméricos similares aos obtidos com o catalisador de 1° Grubbs. Foram realizados estudos para otimizar as condições experimentais nas reações de ROMP, através da análise das estabilidades térmicas dos polímeros obtidos constatou-se a influência das variáveis tipo de catalisador, concentração de catalisador, tempo de reação, número de NBE por estrutura do monômero e a influência da adição de ácido na atividade catalítica dos complexos. Os valores de transição vítreas foram determinados através de DSC, o monômero de partida mostrou uma influência mais significativa sobre o valor de Tg dos polímeros obtidos do que o tipo de catalisador utilizado. Os estudos mecânicos dos materiais resultantes indicaram que foram obtidos desde materiais borrachosos a rígidos alterando a natureza do monômero e o tipo de catalisador utilizado e não foi possível estabelecer uma correlação entre as densidades de reticulação e a quantidade de anéis NBE da estrutura, nas condições analisadas. A cinética do processo de cura foi acompanhada através da ROMP induzida por temperatura, sob diferentes condições de frequência angular, temperatura e tempo. / Polymers with different characteristics were synthesized from the ring opening polymerization (ROMP) of three different monomers of norbornene (NBE) derived with triglycerides or monoglycerides from castor and soybean oils: Norbornene-functionalized castor oil (NCO), Norbornene-functionalized alcohol castor oil (NCA) and the new Norbornene-functionalized epoxidized soybean oil (NESBO). It was used, as catalyst precursors, complexes of the type [RuCl2(PPh3)2(amine)], amine = perhydroazepine and piperidine and the catalyst Grubbs (1st and 2nd generation). The effects of the structure of the monomer and catalyst in the polymerization process, as well as the thermal and mechanical properties of the resulting polymers, were investigated. Through the nuclear magnetic resonance of proton (1H-NMR), it was determined the number of active sites (norbornene units) per chain of fatty acid in each monomer: 1.8 to NCO, 2.6 to NCA and 4.5 to NESBO. The number of monomeric units (active sites for ROMP), as well as the viscosity of each monomer plays an important role in controlling the initiation and propagation of polymerization and the final properties of the polymers obtained. The Ru-amine complex type, produced polymeric materials similar to those obtained with Grubbs catalyst 1st. Studies were performed to optimize the experimental conditions in ROMP reactions, through analysis of the thermal stabilities of the obtained polymers was found to influence the variables: type of catalyst, catalyst concentration, reaction time, number of NBE in structure of the monomer and influence of acid addition on the catalytic activity of the complex. The glass transition values were determined by DSC, the starting monomer showed a more significant influence over the Tg value of all the obtained polymers compared to the all used catalysts. The mechanical studies of the resulting materials indicated that rubbery and rigid materials were obtained, by changing the nature of the monomer and type of catalyst, although it was not possible to determine a correlation between the crosslinking densities and the quantity of NBE rings of the structure for the analyzed conditions. The kinetic for the cure process was followed through the induced ROMP by temperature under different conditions of angular frequencies, temperature, and time.

Essa pesquisa tem como meta estudar a atividade catalítica de complexos do tipo [RuCl2(PPh3)x(BS)] a partir de reações entre [RuCl2(PPh3)3] e os compostos do tipo Base de Schiff (BS) do tipo R1N=CHR2 onde os grupos R1 = cicloexil, fenil ou sec-butil, para aplicações em reações de polimerização via metátese por abertura de anel (ROMP) de norborneno (NBE). As reações foram realizadas na presença de etildiazoacetato (EDA) e os resultados dos complexos foram comparados em relação às características dos polímeros isolados em função da temperatura e do tempo de reação. Os complexos foram caracterizados por análise elementar CNH, espectroscopia na região do infravermelho e UV-Vis, RMN (31P; 1H) e voltametria cíclica. Os poliNBE apresentaram um σc = 0,41 determinado por RMN 13C. Experimentos realizados por 60 minutos a 25 °C na razão [NBE]/[Ru] = 5000 mostraram que o complexo [RuCl(PPh3)2(Ph)(IminCy)] formou 95% de poliNBE, enquanto que o complexo [RuCl(PPh3)2(Ph)(IminPh)] sintetiza 81,4% de NBE. Para o complexo [RuCl(PPh3)2(Ph)(IminBu)] sua atividade em ROMP para o NBE foi de 70,3%. Assim foi comparado a reatividade entre os ligantes Cy, Ph e Bu. Nas mesmas condições, apenas o complexo [RuCl(PPh3)2(Ph)(IminCy)] obteve melhora significativa no rendimento a 50 °C. Foram investigados também os efeitos de agentes promotores como ácido, sal e luz para a viabilização das reações de ROMP. / This research aims to study the activity of[RuCl2(PPh3)x(BS)] complexes by means of [RuCl2(PPh3)3] and Schiff base ligands (BS) R1N=CHR2where R1= cyclohexil, phenil and sec-butil groups, in order to catalyze ring opening metathesis polymerization (ROMP) reactions of norbornene (NBE). The reactions occur in presence of etyldiazoacetate (EDA) and was investigated according to the temperature and the time reaction. The complex was characterized by CNH elemental analysis, infrared, UV-vis spectra, NMR (1H; 31P) and cyclic voltametry. The polymer showed σc = 0,41 by NMR (13C). The experiments performed for 60 minutes at 25 °C with the ratio [NBE]/[Ru] = 5000 showed that [RuCl(PPh3)2(Ph)(IminCy)] complex obtained 95% of polyNBE, while that [RuCl(PPh3)2(Ph)(IminPh)] complex yielded 81,4% of NBE. However, the [RuCl(PPh3)2(Ph)(IminBu)] provided 70,3% of polyNBE. Under same conditions, only [RuCl(PPh3)2(Ph)(IminCy)] complex showed significant changes at 50°C. In addition, promoters agents with acids, salts and light were investigated with the aim at making the ROMP reactions feasible.

Ce travail de thèse consiste à combattre le développement microbien des réservoirs de carburant aéronautiques dont le métabolisme entraine la production d’acides organiques susceptibles de corroder les parois métalliques des réservoirs. Des substances biocides sont habituellement utilisées pour éliminer les populations microbiennes. Ces substances peuvent être des composés organiques ou bien de manière plus courante du chrome (VI) sous forme de revêtement à la surface des parois afin de créer une couche passive et d’empêcher la corrosion chimique. Cependant, le chrome appartient à la catégorie des substances cancérogènes, mutagènes et reprotoxiques et se trouve maintenant soumis à restriction par la réglementation européenne Registration, Evaluation and Authorization of Chemicals (REACh). Pour remplacer les systèmes en place, le choix s’est porté sur la préparation de particules polymères pH-sensibles capables de libérer une molécule biocide en présence de microorganismes. De telles particules sont obtenues par copolymérisation par métathèse de cyclo-oléfines (ROMP) de norbornène avec un macromonomère linéaire de polyglycidol α-norbornenyl. Ce dernier permet d’une part la stabilisation des particules et d’autre part la multifonctionnalisation de l’objet par des molécules de biocide. Celles-ci sont introduites sur la chaîne de polyglycidol via un lien imine pH-sensible par substitution des fonctions hydroxyle par des entités dodécylamine. La libération du biocide à un pH inférieur à 7 a été validée ainsi que les capacités de ces particules à lutter contre des microorganismes tel que Hormoconis resinae souche identifiée comme se développant dans les réservoirs d’avions. Dans une dernière étape, les particules fonctionnalisées dodécylamine ont été incorporées dans un revêtement usuel en aéronautique et la capacité des particules à ne pas altérer la résistance du revêtement de base à des conditions de corrosion extrêmes a permis de vérifier leur applicabilité dans ce domaine. / The aim of this Thesis work was to address the issue of microbial contamination inside fuel tanks. Microorganisms induce the chemical corrosion of airplane tank walls due to their production of organic acids. Biocide compounds are typically used to inhibit these microorganisms, either in the form of organic small molecules, or most commonly as chromium-based coatings on the walls to hinder chemical corrosion. Organic biocides need to be replenished regularly, while chromium is a particularly dangerous compound targeted by the European Registration, Evaluation and Authorization of Chemicals (REACh) legislation due to its carcinogenic nature. A replacement approach selected for this project was the development of a smart system of multifunctional polymeric particles synthesized by dispersion ROMP, which can deliver a biocide following an acidic trigger due to the presence of microorganisms. The polymerization utilized a linear α-norbornenyl-polyglycidol macromonomer as a reactive surfactant. The hydroxyl-rich polyglycidol backbone of the macromonomer was beneficial for the conjugation of dodecylamine through a pH-sensitive imine bond and permitted the preparation of highly functionalized bioactive particles. A proof of concept for the pH sensitivity of the system was provided and the antifungal efficacy of the biocide-functionalized macromonomer and particles was verified. The particles were also integrated in a coating formulation to simulate their application on tank walls. The qualities of the original coating were preserved even after prolonged exposure to corrosive conditions, making this system viable for its foreseen application.

Novos materiais poliméricos foram desenvolvidos utilizando como uma das matérias-primas o óleo de palma (OP). Para tanto, um novo monômero de norborneno, denominado norbornenil óleo de palma (NOP), foi obtido a partir da inserção de norborneno substituído com grupo carboxílico nos triglicerídeos do óleo da palma. O óleo de palma, assim como os produtos de cada etapa de síntese do NOP foram caracterizados por RMN-1H. Foi determinado um teor de 52% de ácidos graxos insaturados no OP, resultando no NOP com 1,0 norborneno por triglicerídeo. Reações de ROMP de NOP com norborneno, na presença de catalisador de Grubbs de segunda geração, resultaram em materiais insolúveis em uma diversidade de solventes polares e apolares. Testes de inchamento em clorofórmio extraíram frações solúveis dos materiais, compostas por poliNBE e unidades NOP não polimerizadas. Dados obtidos por TGA sugerem a presença de cis e trans poliNBE, além de uma etapa de degradação desconhecida, atribuída ao copolímero poli(NOP-co-NBE) o qual seria o componente insolúvel resultante dos experimentos de inchamento. Assim, os materiais desenvolvidos foram classificados como blendas poliméricas de poliNBE e poli(NOP-co-NBE). Foram avaliados os tempos de gelificação de amostras com diferentes concentrações de catalisador e combinações NOP/NBE através de RMN em baixo campo magnético, obtendo-se comportamentos regulares que podem permitir a previsão do tempo de gelificação de outras amostras. A análise da distribuição dos valores de T2 mostrou aumento na rigidez dos materiais finais ao se aumentar o teor inicial de NOP. / New polymeric materials have been developed using palm oil as a raw material. For this, a new monomer of norbornene, called norbornene palm oil (NPO) was obtained from insertion of norbornene containing the carboxylic group in the palm oil triglycerides. Palm oil as well as products of each step NPO synthesis were characterized by 1H-NMR. It was determined 52% unsaturated fatty acids content in the OP, resulting in NPO with 1.0 norbornene per triglyceride. ROMP reactions of norbornene with NPO, in the presence of the Grubbs second generation catalyst, resulting insoluble materials in a variety of polar and nonpolar solvents. Soluble fractions were extracted in swelling, containing polyNBE and unpolymerized NPO units. TGA data suggests the presence of cis and trans polyNBE, plus an unknown degradation step, attributed to poly(NPO-co-NBE) copolymer which would be insoluble component resulted from the swelling experiments. Thus, the developed materials were classified as polymer blends of polyNBE and poly(NPO-co-NBE). The gelation times of samples having different catalyst concentrations and NPO/NBE combinations were evaluated by low magnetic field NMR, obtaining regular behaviors that may allow the gelation time prediction of other samples. The analysis of T2 values distribution showed increased in the stiffness of the final material by increasing the initial NPO content.

Este trabalho foi desenvolvido com o propósito de investigar as reações de polimerização por metátese via abertura de anel (ROMP) assistidas pelos catalizadores desenvolvidos pelo grupo do Prof. Dr. Benedito dos Santos de Lima Neto do Instituto de Química de São Carlos (IQSC-USP), usando métodos computacionais de mecânica quântica. Portanto, este projeto foi uma combinação de resultados teóricos e experimentais. No capítulo 1, foi elucidado o mecanismo principal da reação de ROMP de norborneno por meio do iniciador catalítico [RuCl2(PPh3)2(piperidina)]. O estudo mostrou que a primeira etapa da reação implica numa associação entre o complexo iniciador e o diazoetanoato de etila (EDA), resultando na formação de uma ligação metalcarbeno. Então, essa espécie perde duas moléculas de trifenilfosfina nos passos subsequentes, sendo que a etapa determinante da velocidade da reação está associada com a saída da segunda molécula de PPh3 devido ao sinergismo eletrônico envolvendo este ligante e a molécula de piperidina. Logo após a etapa determinante da velocidade, ocorre a coordenação de uma molécula de norborneno e um similar efeito trans-sinérgico entre este monômero e o ligante piperidina ativa a catálise. No capítulo 2 está descrito o estudo do mecanismo de uma série de complexos de fórmula [RuCl2(PPh3)2(amina)] (amina = pirrolidina, piperidina, azepano, azocano). Estas aminas cíclicas possuem volumes moleculares que aumentam no sentido da pirrolidina ao azocano. A troca dessas aminas afeta substancialmente o comportamento termodinâmico desses complexos através da combinação de efeitos eletrônicos e estéricos. A investigação realizada para os compostos dessa série levou ao mesmo mecanismo elucidado para o complexo contendo piperidina e com os mesmos processos mais relevantes que são as saídas dos ligantes trifenilfosfinas. Notou-se que a formação do isômero PBQ fica comprometida ao passo que a amina no complexo [RuCl2(PPh3)2(amina)] vai ficando mais volumosa devido ao maior espaço ocupado ao redor do metal na posição apical da pirâmide de base quadrada (PBQ) e que representa uma tensão considerável na estrutura do complexo que tende a se converter, preferencialmente, à geometria bipirâmide trigonal (BpT), como acontece com o complexo iniciador [RuCl2(PPh3)2(azocano)]. Observou-se também que a saída da primeira fosfina é influenciada pelo efeito estérico provocado pela amina. Em contrapartida, a saída da segunda já é um processo regido eletronicamente e é influenciado pela capacidade doadora da amina trans-posicionada ao ligante PPh3 em um dos intermediários que é formado durante a reação. No capítulo 3 está descrita a investigação da reação de ROMP com o complexo iniciador [RuCl2(PPh3)2(piperidina)] usando as moléculas diazoetanoato de etila (EDA), diazoetanoato de benzila (BDA) e diazoetanoato de terc-butila (TDA) como fontes de carbeno para gerar a espécie in situ [Ru(=CHR)Cl2(PPh3)2(piperidina)]. Curiosamente, a troca dos carbenos também não afetou o mecanismo proposto inicialmente para a série das aminas. Os perfis termodinâmicos traçados para esses diferentes carbenos mostram que o complexo contendo o carbeno etanoato de benzila-1-ilideno (EBI) foi o que mais se diferiu, seguindo uma tendência termodinâmica distinta para a saída dos ligantes trifenilfosfina. Para as demais etapas, os três complexos apresentaram um comportamento bastante similar. O estudo dessa série mostrou-se ser mais intricado do que a série das aminas, pois esses carbenos podem afetar tanto eletrônico quanto estericamente a estrutura dos compostos em diferentes etapas do mecanismo que ainda não foram investigadas minunciosamente. / This work was developed with the purpose of investigating the ring-opening metathesis polymerization (ROMP) with catalysts developed in the research group of Prof. Dr. Benedito dos Santos Lima Neto of the Institute of Chemistry of São Carlos (IQSC-USP) by computational methods of quantum mechanics. Therefore, this project was a combination of theoretical and experimental results. In Chapter 1, the main mechanism of ROMP reaction of norbornene by the initiator complex [RuCl2(PPh3)2(piperidine)] was elucidated In this investigation, the first reaction step involves an association between the initiator complex and ethyl diazoacetate (EDA), resulting the formation of metalcarbene bond. Then, this species loses two triphenylphosphine ligands in the subsequent steps and the rate reaction is associated with the loss of the second molecule due to the electronic PPh3 synergism involving this ligand and the piperidine molecule. Immediately after the rate reaction step, the coordination of norborneno occurs and a similar trans synergistic effect between the monomer and piperidine ligand actives the catalysis. Chapter 2 describes the study of the mechanism of complexes type [RuCl2(PPh3)2(amine)] (amine = pyrrolidine, piperidine, azepane, azocane). These cyclic amines have molecular volumes that increase from pyrrolidine towards azocane. The exchange of amines affects substantially the thermodynamic behavior of these complexes by a combination of electronic and steric effects. The four compounds showed the same mechanism elucidated for the complex containing piperidine. It was noted that the formation of the PBQ isomer is avoided while the amine in the complex [RuCl2(PPh 3)2(amine)] becomes more voluminous. It was also observed that the loss of the first phosphine is influenced by the steric effect caused by the amine. In contrast, the loss of the second (phosphine) is already a process electronically-governed, and is influenced by the donor capacity of the amine ligand trans-positioned to PPh3 in one of the intermediate that is formed during the reaction. The Chapter 3 describes the investigation of the ROMP reaction using the initiator complex [RuCl2(PPh3)2(piperidine)] with the molecules ethyl diazoacetate (EDA), benzyl diazoacetate (BDA) and tert-butyl diazoacetate (TDA) to generate the carbene species [Ru(=CHR)Cl2(PPh3)2(piperidine)] in situ. Interestingly, the exchange of carbenes did not affect the mechanism originally proposed for the series of amines complexes. The complex containing the carbene ethanoate benzyl-1-ylidene (EBI) was what showed the most different thermodynamic profile from the others, following a distinct thermodynamic tendency for the loss of triphenylphosphine ligands. For the remaining steps, the three complexes showed a very similar behavior. The study of this series proved to be more intricate, because these carbenes may affect as much as sterically electronic structure of the compounds at different stages of the mechanism.

This thesis describes studies directed to the ring opening metathesis polymerisation (ROMP) of some fluorinated compounds using a range of well-defined initiators. Chapter 1 reviews some general aspects of olefin metathesis and ring opening metathesis polymerisation of relevance to the work described in this thesis. Topics such as piezo- and pyro-electricity and optical and electrical properties of conjugated polymers are introduced and these receive more detailed attention later in the thesis. Chapter 2 describes the synthesis, characterisation and properties of . poly(bis(trifluororaethyl)norbomadiene) in detail. The use of various initiating systems that have been used previously and the effect they have on the tacticity of the resulting polymer raicrostructure are discussed. The latter part of this chapter reviews some of the current thinking concerning the detailed mechanistic aspects of this polymerisation. Chapter 3 reviews attempts directed to an improvement in tacticity control in the synthesis of poly(bis(trifluoromethyl)norbomadiene). The synthesis and activity of the new well-defined initiators used in these studies are reported. It is shown that varying the nature of the ancillary Ligands surrounding the metal centre can have a dramatic influence on the tacticity of the resulting polymer. Chapter 4 reports studies directed to an examination of the limits of the well controlled synthesis of poly(bis(trifluoromethyl)norbornadiene). The syntheses of high trans and high cis, highly tactic poly(bis(trifluoromethyl)norbornadiene samples using well-defined initiating systems are described. It is shown that by varying the monomerinitiator ratio, samples with a wide range of molecular weights can be achieved and these are reported. Chapter 5 describes experiments concerning the ROMP of fluorinated monomers containing six membered rings. In particular ROMP studies of the monomers, 2,3-bis(trifluoromethyl)bicyclo[2.2.2]octa-2,5-diene . and 2,3- (tetrafluorobenzo)bicyclo[2.2.2]octatriene are described finally, Chapter 6 provides a summary of the work reported and outlines some ideas for future studies.

Plastics have changed the world of materials due to their high durability, low price, low density, and ease of processing. Unfortunately, the majority of plastic goods produced are discarded instead of recycled, leading to a massive accumulation of plastic waste in landfills and natural habitats. To decrease the impact of plastic waste, sustainable materials and synthetic methods are needed. This dissertation focuses on new strategies for developing renewable and degradable polymers with minimal energy input as well as new methods to blend legacy polyolefins with renewable polymers. The first half of the dissertation focuses on synthesizing polymers using light while the second section focuses on combining traditional polyolefins with renewable polymers. Photo-mediated polymerizations are an attractive alternative to traditional thermal polymerizations due to their ease of setup and the spatiotemporal control afforded by light. Using LED lights also affords a synthetic technique that requires little energy input, thus decreasing the overall environmental impact of the material. In this work, coupling LEDs with a trithiocarbonate allowed for the synthesis of many different polymers and topologies. Bottlebrush polymers synthesized with light afforded molar masses in excess of 11 million Da without the oligomerization of the bottlebrush polymers. These bottlebrush polymers were then used to make reversibly crosslinkable adhesives, allowing for a new example of recyclable adhesives. The second half of the dissertation focuses on developing sustainable polymers using ring-opening metathesis polymerization (ROMP) to combine the properties of polyolefins with renewable polymers. First, polyketones synthesized by ROMP were developed for their potential use as photodegradable polymers. This initial study probed the synthesis of different polyketone monomers and the properties of their respective polymers. Next, a photodegradable and biodegradable thermoplastic elastomer (TPE) was synthesized that incorporated a ketone containing polybutadiene (PB) flanked by polylactide (PLA). The thermomechanical properties were controlled based on the relative length of each block while the rate of photodegradation was controlled by the mol% of ketone incorporated into the PB block. Finally, ABA triblock copolymers of cellulose derivatives and polyolefins were developed for their uses as compatibilizers for blends. With the addition of as little as 1 wt% of the ABA triblock copolymer, the respective blends showed large imp / PHD

Phthalocyanines (Pcs) are highly conjugated, 18π-electron cyclic molecules composed of four isoindoline units that exhibit unique optical, electrical and chemical properties. While originally used as dyes and pigments, the use of Pcs in modern technology has increased dramatically due to improved understanding and processing capabilities. Work in this dissertation outlines a number of methods to prepare Pc-containing materials for use in various applications. Chapter 1 provides a brief review of methods used to prepare Pc-containing polymeric materials from both symmetric and asymmetric macrocycles. Discussion will focus on methods that incorporate symmetric Pcs as the focal point, with particular attention being paid to the influence of the peripheral substitution of the Pc on macromolecular structure and properties. Further discussion will focus on the utilization of asymmetric Pcs as auxiliary functionalities, such as at the terminus or as pendant groups, of larger macromolecular materials. Chapter 2 describes the preparation of linear Pc-containing polymers through ring-opening metathesis polymerization of a Pc monomer. Through proper selection of catalyst, well-defined polymers with Pcs as pendant groups were prepared. Due to the controlled nature of ROMP, polymers of varying architectures, composition, and size were synthesized. The effect of Pc metallation, polymer composition and architecture on the site-isolation of the chromophore was investigated in both solution and condensed-phase thin films. Chapter 3 reports on efforts to prepare linear polymers with companion functionalities for post-polymerization coupling of asymmetric Pcs. Polymers with pendant furan groups were prepared for coupling with asymmetric Pcs through Diels-Alder cycloaddition. Investigation indicated that while coupling was achievable, the presence of the Pc in the resultant polymer promoted undesired crosslinking when stored at ambient conditions in light. Attempts to mitigate this problem through alternation of functionality locations were attempted by placing the furan functionality on the Pc, but degradation of the furan occurred to quickly to perform coupling sufficiently. Chapter 4 discusses the preparation of Pc-containing networks through Diels-Alder cycloaddition of furan and maleimide containing tetrasubstituted Pcs. Following preparation of the various Pcs, network formation in various states was conducted including solution, molded thick films, and patterned assemblies. Chapter 5 summarizes the results presented in Chapters 2-4 and provides an outlook for some future directions based upon the work herein. In addition, some preliminary results of some of these directions will also be presented.