Research into inorganic supramolecular chemistry is burgeoning, in particular that which focuses on the formation of capsular molecules and the effects that these unique environments have on catalytic reactions. With the aim of producing new ligand designs that could not only support reactive metals, but also partake in supramolecular aggregation to provide a capsular microenvironment, new tripodal ligands and wide span imines and amines have been synthesised. Furthermore, the exploitation of hydrogen-bonding motifs formed through pyrrole-imine tautomerisation upon metallation of these ligands has been explored, with the aim of enhancing reactivity and stabilising reactive intermediates. In Chapter one, the concept of covalent and non-covalent capsules is introduced, and includes the different aspects affecting the encapsulation of molecules and their use as nanoreactors. The use of secondary interactions, e.g. hydrogen-bonding in metal complexes of tetrapodal and tripodal ligands is discussed. Chapter two describes the synthesis of a tripodal pyrrole-imine ligand and the formation of its multi-metallic complexes of Group one metals, transition metal and the f-block elements. The complete and partial tautomerisation of this ligand upon metal complexation is also examined. In Chapter three, the formation of hangman complexes of the tripodal pyrrole-imine ligand is described and is extrapolated to the chemistry of a new pyrrole-amide ligand. The synthesis of this latter ligand and its properties with regards to anion binding are also explored. Chapter four describes the formation of wide span diamine and diimine ligands and their propensity to form adducts with cobalt and zinc chlorometallates and unusual multimetallic palladium complexes. The final conclusions of the work presented in this thesis are drawn in Chapter five. Chapter six presents experimental details and characterising data for all of the new compounds presented in this thesis.

The chloro and pyridinate derivatives of rhenium(I) tricarbonyl complexes containing the diimine ligands 2,2’-bipyrazine (bpz) and 5,5’-dimethyl-2,2’-bipyrazine (Me2bpz) are discussed. When compared to similar rhenium(I) tricarbonyl complexes of 2,2’-bipyridine (bpy) and 2,2’-bipyrimidine (bpm), the Me2bpz complexes are comparable to bpm derivatives and their properties are intermediate between those of bpy and bpz complexes. Also discussed is the synthesis and properties of two new analogues of ruthenium(II) tris-bipyridine, a monomer and dimer. The complexes contain the ligand 6,6’-(1,2-ethanediyl)bis-2,2’-bipyridine (O-bpy) which contains two bipyridine units bridged in the 6,6’ positions by an ethylene group. Crystal structures of the two complexes formulated as [Ru(bpy)(O-bpy)](PF6)2 and [(Ru(bpy)2)2(O-bpy)](PF6)4 reveal structures of lower symmetry than D3 which affects the electronic properties of the complexes as revealed by Density Functional Theory (DFT) and Time Dependent Density Functional Theory (TDDFT) calculations. Iron(II) tris-bipyrazine undergoes dissociation in solution with loss of the three bipyrazine ligands. The rate of the reaction in acetonitrile depends on the concentration of anions present in the solution. The rate is fastest in the presence of Cl- and slowest in the presence of Br-. In a second discussion DFT calculations are used to explore four iron(II) diimine complexes. DFT calculations show the higher energy HOMO (highest occupied molecular orbital) orbitals of the four complexes are metal centered and the lower energy LUMO (lowest unoccupied molecular orbitals) are ligand centered. / Dissertation(Ph.D.)--Wichita State University, College of Liberal Arts and Sciences, Dept. of Chemistry

N,N&rsquo / -bis(ferrocenylmethylene)ethylenediamine was prepared from the reaction of ferrocenecarboxaldehyde and ethylenediamine and characterized by IR, Raman, 1H and 13C-NMR spectroscopy. The electrochemical behaviour of this ligand was also studied for the first time by cyclic voltammetry. Diferrocenyl diimine ligand was used in the thermal substitution of 1,5-cyclooctadiene in Cr(CO)4(2:2-1,5-cyclooctadiene) at 38&deg / C in toluene for two hours to form the tetracarbonyl[N,N&rsquo / -bis(ferrocenylmethylene)ethylenediamine]chromium(0), [Cr(CO)4(BFEDA)]. This complex was succesfully isolated and crystallized from its 1:1 toluene/dichloromethane solution and characterized by elemental analysis, MS, IR, 1H, 13C-NMR spectroscopy. Electrochemical behaviour of the complex was also studied by cyclic voltammetry and the mechanism of electrode reaction was investigated by in-situ UV-VIS and IR spectroscopy measurements. This new complex has the iron atom of ferrocene unit in conjugation with the chromium metal center and, therefore, shows an electronic communication between two metal atoms.

Submitted by Beatriz Aline Riga null (beatriz_aline16@hotmail.com) on 2017-03-15T18:07:31Z No. of bitstreams: 1 Riga Rocha, B. A._me_sjrp.pdf: 4397938 bytes, checksum: 97cd69af09e5df0e1dcc372a541946c2 (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2017-03-21T16:17:50Z (GMT) No. of bitstreams: 1 rocha_bar_me_sjrp.pdf: 4397938 bytes, checksum: 97cd69af09e5df0e1dcc372a541946c2 (MD5) / Made available in DSpace on 2017-03-21T16:17:50Z (GMT). No. of bitstreams: 1 rocha_bar_me_sjrp.pdf: 4397938 bytes, checksum: 97cd69af09e5df0e1dcc372a541946c2 (MD5) Previous issue date: 2017-02-22 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste trabalho objetivou-se a síntese e caracterização de oito complexos de cobalto(II) que fossem aptos a atuarem como agentes controladores na Polimerização Radicalar Mediada por Cobalto do monômero acetato de vinila. Através da modulação da esfera de coordenação destes complexos com a alteração dos efeitos estéricos e eletrônicos promovidos pela coordenação de ligantes α-diiminas, buscou-se estabelecer parâmetros para propor a forma como estes complexos mediam a CMRP do referido monômero. Os complexos foram divididos em dois grupos, objetivando uma avaliação mais eficiente da forma como os efeitos estéricos e eletrônicos interferem na capacidade controladora dos mesmos. Após a variação sistemática das proporções molares entre complexo, iniciador e monômero encontrou-se na proporção [Co]/[AIBN]/[VAc] = 1/3,25/542 os resultados mais satisfatórios deste trabalho. O uso de DMSO fora prejudicial para os complexos 2a-c, porém fez com que os complexos 2d-h apresentassem melhorias, reduzindo seus valores de polidispersidade e aumentando as massas moleculares dos polímeros. O complexo 2b fora escolhido como o melhor controlador do grupo do efeito estérico, por reunir em si as características estérias e eletrônicas que o fizeram apresentar os menores valores de polidispersidade (Đmáx = 1,43). Com relação ao grupo de complexos do efeito eletrônico, fora o complexo 2f que, devido à maior estabilidade estrutural conferida ao complexo por seu substituinte cicloexil, apresentara as menores polidispersidades de seu grupo, entre 1,12 e 1,58. / This work aimed the synthesis and characterization of eight cobalt(II) complexes which could be able to act as controlling agents in vinyl acetate radical polymerization mediated by cobalt. By modulating the coordination sphere of these complexes, modifying the steric and electronic effects offered by the α-diimine ligands, we sought to establish parameters to propose how these complexes mediate the CMRP of vinyl acetate. The complexes were split in two groups in way to assess efficiently how the electronic and steric effects can affect the controlling capacity of the CoII(α-diimine).A systematic variation of the molar ratio such as [Co]/[initiator] and [Co]/[monomer] made it possible to choose [Co]/[initiator]/[monomer] = 1/3.25/542 as the ratio that provided certain level of control. The addition of DMSO was detrimental to the complexes 2a-c, but caused an improvement to the activity of complexes 2dh, reducing their polydispersity values and increasing the molecular weights of the polymers. Complex 2b was chosen as the best controller of the steric effect group, its steric and electronic characteristics made possible to reach the lowest polydispersity of its group (Đmax = 1.43).Regarding to the group of complexes of the electronic effect, it was the complex 2f that had the smallest polydispersity of its group, between 1.12 and 1.58, due to the greater structural stability conferred to the complex by its cyclohexyl substituent.