Thesis (Ph.D.)--Drexel University, 2009. / Includes abstract and vita. Includes bibliographical references (leaves 201).

This Thesis describes the synthesis and characterisation of new alkaline earth metal and aluminium gallyl complexes. Experimental studies were performed to investigate their structure. The reactivity of these species was also studied. <b>Chapter 1</b> introduces metal-metal bonded complexes containing alkaline earth metals and aluminium and the use of gallium(I) analogues of N-heterocyclic carbenes in the synthesis of heterobimetallic complexes of gallium. <b>Chapter 2</b> describes the synthesis and reactivity of alkaline earth gallyl complexes supported by beta-diketiminate ligands. <b>Chapter 3</b> presents the synthesis and reactivity of alkaline earth gallyl complexes supported by the carbazolide ligand CzOx. <b>Chapter 4</b> describes synthesis of aluminium-gallium bonded complexes supported by amidinate and b-diketiminate ligands and the attempted study of their reactivity. <b>Chapter 5</b> presents full experimental procedures and characterising data for the new complexes reported.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Neste trabalho descreve-se a sÃntese, caracterizaÃÃo, reatividade e propriedades de novos complexos de rutÃnio com os ligantes o-fenilenodiamina, o-aminofenol, catecol, naftalenodiol, dopamina e adrenalina a partir do complexo precursor mer-[RuIIICl3(dppb)(H2O)]. Descreve-se tambÃm uma nova rota de desidrogenaÃÃo oxidativa do ligante o-fenilenodiamina a partir da interaÃÃo deste com o complexo mer-[RuIIICl3(dppb)(H2O)]. O complexo mer-[RuIIICl3(dppb)(H2O)] à extremamente versÃtil como precursor. Ao reagir com o ligante o-fenilenodiamina diretamente, forma uma mistura constituÃda por complexos que contÃm as formas oxidada (bqdi) e reduzida (opda) do ligante o-fenilÃnico, os complexos trans-[RuIICl2(dppb)(bqdi)] e trans-[RuIICl2(dppb)(opda)], que foi confirmada pela observaÃÃo de dois singletos em d 47 e d 26 no espectro de RMN 31P{1H}. Uma tentativa de atribuiÃÃo preliminar sugere que o ligante opda à oxidado a bqdi durante a reaÃÃo, conforme mecanismo proposto no presente trabalho. Entretanto, o produto obtido da reaÃÃo entre o ligante o-fenilenodiamina e o complexo mer-[RuIIICl3(dppb)H2O] por meio da lenta adiÃÃo do ligante apresentou apenas um sinal em d 26 no espectro de RMN 31P{1H}, indicando que o complexo trans- [RuIICl2(dppb)(bqdi)] à preferencialmente formado. Tal complexo foi caracterizado por anÃlise elementar, tÃcnicas espectroscÃpicas e eletroquÃmicas e sua estrutura determinada por difraÃÃo de raios X. Com o objetivo de reforÃar o mecanismo proposto, realizou-se a sÃntese entre o o ligante o-fenilenodiamina e o complexo [RuIICl2(dppb)(PPh3)]. Neste caso, o centro metÃlico de rutÃnio jà se encontra no estado reduzido e o metal nÃo promoverà nenhum tipo de mudanÃa no estado de oxidaÃÃo do ligante. Portanto, o produto obtido apresentou apenas um sinal em d 47 no espectro de RMN 31P{1H}, indicando a formaÃÃo do complexo trans-[RuIICl2(dppb)(opda)], caracterizado por microanÃlise, tÃcnicas espectroscÃpicas e eletroquÃmicas e cuja estrutura foi determinada por difraÃÃo de raios X. Os complexos isolados do tipo trans-[RuIICl2(dppb)(X)], onde X = quinona, dopamina e adrenalina e cis-[RuIICl2(dppb)(L)], onde L = o-aminofenol na forma quinonÃide e bqdi, foram caracterizados por espectroscopia eletrÃnica, vibracional e de ressonÃncia magnÃtica nuclear de fÃsforo, alÃm de tÃcnicas eletroquÃmicas, como voltametria cÃclica e de pulso diferencial. / This research work describes the synthesis, characterization, reactivity and properties of new complexes of ruthenium with the ligands o-phenylenediamine, oaminophenol, catechol, naphtalenediol, dopamine and adrenaline and the mer-[RuIIICl3(dppb)(H2O)] complex. Also, it describes a new metal-assisted oxidative dehydrogenation of the interaction o-phenylenediamine ligand and the mer- [RuIIICl3(dppb)(H2O)] complex. The mer-[RuIIICl3(dppb)(H2O)] complex has shown to be a versatile compound as starting material. The reaction of this compound with the o-phenylenediamine ligand produced a mixture of compounds with the bqdi and opda forms of the o-phenylene ligand, the trans-[RuIICl2(dppb)(bqdi)] and trans-[RuIICl2(dppb)(opda)] complexes, that it was confirmed for the observation of two singlet signals at d 47 and d 26 in the 31P{1H} NMR spectrum. One very first assignment suggests that the opda ligand is oxidized to bqdi form during the reaction, according to mechanism proposed in this work. However, the product of the reaction between the o-phenylenediamine ligand and the mer-[RuIIICl3(dppb)H2O] complex by the slow addition of the ligand showed only one signal at d 26 in the 31P{1H} NMR spectrum, indicating that the trans-[RuIICl2(dppb)(bqdi)] complex is preferentially produced. This complex was characterized by the elemental analysis, spectroscopic and electrochemical techniques and its structure has been determined by X-ray crystallography. Aiming to reinforce the proposed mechanism, we conducted the reaction of the o-phenylenediamine ligand with the [RuIICl2(dppb)(PPh3)] complex. Since the ruthenium metal center is already in the reduced state, it will not promote any redox change in the ligand. Thus, the complex produced showed only one signal at d 26 in the 31P{1H} NMR spectrum, indicating the formation of the trans-[RuIICl2(dppb)(opda)] complex that it was characterized by the elemental analysis, spectroscopic and electrochemical techniques and its structure has been determined by X-ray crystallography. The compounds isolated of type trans-[RuIICl2(dppb)(X)], X = quinone, dopamine and adrenaline and cis-[RuIICl2(dppb)(L)], L = o-aminophenol in the quinonoide form and bqdi, were characterized by the spectroscopic and electrochemical techniques.