A series of conformationally constrained 2,6-bisferrocenylphenyl thioethers were synthesized via Suzuki-Miyaura cross coupling reactions. Structural information was obtained using X-ray crystallography and dynamic ¹H NMR spectroscopic studies, showing highly constrained m-terphenyl systems. Interaction of the ferrocene moieties through space mediated by the sulfur were studied by ultra-violet photoelectron spectroscopy (UPS), cyclic voltammetry, differential pulse voltammetry, UV-Vis-NIR spectroscopy and DFT computations. Electrochemical results show two, fully reversible 1e⁻ redox processes for the ferrocenes where the separation of peaks is affected by both solvent and supporting electrolyte, suggesting significant electrostatic interaction which is further confirmed in the gas phase by UPS studies. To determine if these interactions could be observed at greater distances, extended m-terphenyl complexes were shown in which 2-sulfur and 3-aromatic moieties were synthesized using a developed selective Suzuki-Miyaura monocoupling procedure in good yields. In these systems, interaction was not observed by electrochemistry or UPS. This suggests the distance between redox centers (~16 Å) is too great for electrostatic interaction, even though there is enhanced interactions observed in the truncated systems. Two new bisferrocenylphenylsulfoxides were also synthesized and studied to determine the effect of the polar sulfoxide bond on through space interaction between the ferrocene moieties. The electronic and redox properties of these compounds were studied by ultra-violet photoelectron spectroscopy, cyclic voltammetry, differential pulse voltammetry, and DFT computations. Electrochemical results for 2,6-bis(ferrocenyl) thioanisole S-oxide show two, fully reversible one electron redox processes. The initial oxidation shows a 62 mV negative shift compared to the sulfide analog 2,6-bis(ferrocenyl)thioanisole, and an increased peak separation for the oxidations of 160 mV. No peak separation is observed in the extended sulfoxide system. No intervalence charge transfer band was observed in the truncated sulfoxide complex by monitoring the UV-Vis/NIR spectroscopy of the mixed valence complex, ruling out electronic communication. Thus, the through space electrostatic interactions of the sulfoxide causes the non-equivalent ferrocenes in the truncated system to have different oxidation potentials. Synthesis was developed towards the synthesis of 1,8-bisferrocenyl-9-(alkylthio) anthracene complexes. It was observed that due to steric congestion at the C9 position of the anthracene scaffold, standard thionation reactions did not proceed as expected. Instead, the reaction of 1,8-dibromo-9-anthrone with Lawesson reagent afforded the intramolecular nucleophilic aromatic substitution cyclization product in quantitative yields. The reaction of the same anthrone under studied dithioketal formation conditions led to sulfur-rearrangement, giving the undesired 1,8-bisferrocenyl-10-(ethylthio)anthracene derivative, as confirmed by X-ray crystallography. Attempted Newman-Kwart rearrangement of 1, 8-dibromoanthracen-9-yl) dimethylcarbamothioate afforded no significant observed product formation, and decomposition of starting materials when heated for extended times. 1,8-bisferrocenyl-9-(methoxy)anthracene was synthesized and structurally characterized by dynamic X-ray crystallography to confirm connectivity. Electrochemical experiments show 2 reversible redox processes separated by 115 mV. Chemical oxidation experiments show unexpected, strong electronic coupling in the mixed valence complex. This coupling was characterized by near-IR absorption at 941 nm, indicating intervalence charge transfer (IVCT). Single electron reduction of 1,8-bisferrocenyl-9-(methoxy)anthracene, followed by quenching with various electrophiles afforded an inseparable mixture of products, one of which was identified by mass spectrometry as the desired 1,8-bisferrocenyl-9-(methylthio)anthracene product. However, this complex was not separable from the mixture and further characterization was not possible. All other routes attempted to incorporate sulfur into the system afforded no conversion of starting materials or decomposition of the reaction mixture.

The synthesis, structure, and reactivity of some organometallic-fusedheterocycles were studied. This work was divided into three parts: first,thiapentalenyl tricarbonyl manganese complexes [Mn(CO)3{??5-SC7H3-1,3-(R)2}]were synthesized employing thiation on diacyl precursors; second, attempts toform the 5,5-fused ring pyrrole analogs to the thiapentalenyl complexes led to theformation of various amine and imine ligands and manganese complexes, but notthe desired ring-closed pyrroles; third, reductive amination on a ferrocenylmonoaldehyde substrate led to the formation of di(N-(ferrocenylmethyl))-Nmethylamineand its cyanoborane and cyanoborohydride analogs.Isolation of the desired thiapentalenyl manganese complexes wasaccomplished by first forming 1,2-diacylcyclopentadienes (fulvenes), convertingto the corresponding thallium salts [Tl{1,2-C5H3(COR)2}] employing thalliumethoxide, transmetallating with [Mn(CO)5Br], and ring closing using either P4S10or Lawesson's Reagent. Ring closure from the diacylmanganese complexes[Mn(CO)3{??5-1,2-C5H3(COR)2}] gave air stable thiapentalenyl complexes inmoderate to good yield and was tolerable to a variety of functional groups (aryl,arylacetyl, t-butyl). In the cases where 1,2-diarylacetyl complexes wereemployed, the isolated products were "quinoidal". While ring closure on thecorresponding diacylrhenium tricarbonyl complexes was not feasible, it wasobserved that these quinoidal thiapentalenyl structures could be formed on aruthenium Cp* moiety using the arylacetyl fulvenes.Various keto-amines or enol-imines could be formed from the 1,2-dibenzoyl fulvene employing primary amines (R = H, Me, OH, OMe). In thepresence of a reducing agent, neither reduction nor ring closure was observedfor any of the cases investigated. Formation of the corresponding manganesetricarbonyl complex for the methyoxyimine case was accomplished by reaction ofthe enol-methoxyimine with thallium ethoxide and then transmetallating with[Mn(CO)5Br]. Reaction of this keto-imine complex with various reducing agentsdid not lead to the desired 5,5-fused ring pyrrole complex but to reduction to thecorresponding alcohol.Diferrocenylmethyl methylamine complexes were obtained by reaction offerrocene monoaldehyde with ferrocenylmethyl methylamine in the presence of amild reducing agent (NaCNBH3). Isolation under anhydrous conditions gave theunexpected cyanoborohydride salt, di(N-(ferrocenylmethyl))-N-methylammoniumcyanoborohydride. Aqueous work-up gave the corresponding free amine.Conversion of the cyanoborohydride salt to the corresponding cyanoborane,di(N-(ferrocenylmethyl))-N-methylammonium–cyanoborane, was accomplishedby refluxing the cyanoborohydride salt in THF.

No description available.

In this research the environmental effects related to the position of a redox moiety with the electrochemical double layer were studied. This project was made possible with the synthesis of a series of lengths of ferrocene derived alkanethiols, a series of lengths of ferrocene derived norbornylogous bridges and a series of lengths of anthraquinone derived norbornylogous bridges. The series of ferrocene derived alkanethiols were used to study the effect of gradually varying the polarity of the self-assembled monolayers (SAMs) surface on the standard electron transfer rate constant and formal potential. This was achieved by varying the portion of hydroxyl to methyl terminated alkanethiol diluent in the SAM preparation step. It was found that the formal potential increased with a decreasing proportion of hydroxyl terminated diluent and increasing length of the diluent. For pure hydroxyl terminated diluent the formal potential was relatively independent of length. It was found that the rate constant increased for short alkane chain lengths with decreasing proportion of hydroxyl terminated diluent. However, it decreased in magnitude with long alkane chain lengths for low proportions of hydroxyl terminated diluent. The norbornylogous bridges were shown to stand proud above the diluent with a similar tilt angle as the alkanethiol diluent. The ferrocene derived norbornylogous bridges showed hydroxyl terminated monolayers had a slower rate constant then methyl terminated diluents independent of length and that it is highly probable that an alkane bridged redox moiety is located very close to the surface of the monolayer. SAMs were created with the ferrocene of the ferrocene derived norbornylogous bridges located at various heights above the monolayers surface. This was done by using various lengths of hydroxyl terminated diluent. It was found that the rate constant and the formal potential decreased with height above the surface. Interfacial potential distribution was used to account for this and to estimate a ??true?? formal potential. The anthraquinone derived norbornylogous bridges were tested at various pH values and heights above the surface. It was found that an accurate estimate for the electron transfer mechanism can not be made for surface bound species due to the effects of interfacial potential distribution. They demonstrated a novel technique for estimating the point of zero charge of the electrode.

Title from PDF of title page (University of Missouri--Columbia, viewed on Feb. 23, 2010). The entire thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file; a non-technical public abstract appears in the public.pdf file. Dr. Steven W. Keller, Dissertation Supervisor. Vita. Includes bibliographical references.

Nesta dissertação o processo de adsorção da tiossemicarbazona do formilferroceno (TFF) em eletrodos de prata e ouro, em soluções aquosas 0,1 mol.L-1 de KCl e de acetonitrila. 0,1 mol.L-1 de NaClO4, foi caracterizado através da técnica espectroscópica SERS. Verificou-se através das variações espectrais que a adsorção da TFF ocorre através dos átomos N1 do grupo imínico e do S do grupo tiocarbonílico. Os processos faradáicos do TFF foram monitorados pela técnica SERS e de absorção no UV-visível. Os espectros SERS para potencial de -1,4 V (Ag/AgCl) sugerem a formação de um novo composto, produto de redução da TFF, o aminometilferroceno. Através da técnica de absorção no UV-visível verificou-se, neste potencial, o aparecimento no espectro de absorção de uma nova banda em 240 nm, atribuída à formação de tiouréia. A identificação deste dois produtos de redução indica que, para o composto TFF, o mecanismo geral de redução dos derivados de tiossemicarbazonas é obedecido. Nenhuma variação espectral, tanto utilizando a técnica SERS como a absorção no UV-visível, foi detectada durante o processo redox FeII/FeIII (E1/2=0,55 V). Os comportamentos de adsorção e faradáico da tiossemicarbazida (TSC), em eletrodo de prata em soluções aquosas neutra e ácida, foram estudados através da técnica SERS. Verificou-se que em meios neutro e ácido, a TSC está adsorvida na configuração cis para potenciais próximos de 0,0 V, interagindo com a superfície através do átomo de S do grupo tiocarbonílico e dos átomos de H ligados ao N1 hidrazínico, através da formação de pares iônicos com os ânions Cl- adsorvidos. Para potenciais mais negativos, os íons cloreto deixam a superfície e a TSC sofre reorientação, assumindo a conformação trans. Não foi observado através da técnica SERS nenhum processo faradáico em solução ácida para potenciais negativos, como havia sido proposto na literatura. A não redução do composto foi confirmada através da técnica de eletroforese capilar. Foi estudado o comportamento Raman ressonante da TFF, verificando-se a ocorrência de um mínimo no perfil de excitação experimental devido à interferência destrutiva das transições dos grupos tiossemicarbazona e ferrocenil. Os perfis de excitação teóricos foram calculados utilizando o método da transformada e os resultados dos ajustes obtidos indicam que existe considerável distorção dos modos do grupo ferrocenil na transição eletrônica em 312 nm, atribuída a n-p* do grupo tiossemicarbazona, caracterizando uma grande interação eletrônica entre os cromóforos da TFF. Para comparar o comportamento Raman ressonante do TFF com o do ferroceno, os espectros Raman ressonante deste composto foram obtidos. Verificou-se que o ferroceno apresenta, também, o efeito Raman anti-ressonante, mas as bandas vibracionais do ferroceno apresentam perfis distintos dos apresentados no composto TFF, indicando que a incorporação do grupo tiossemicarbazona no anel ciclopentadienil modifica a estrutura eletrônica do grupo ferrocenil. / In this dissertation, the adsorption process of the formylpyridine thiosemicarbazone (TFF) at silver and gold surfaces in aqueous and in acetonitrile solutions has been characterized by using the SERS (Surface-enhanced Raman Scattering) technique. It has been verified that TFF adsorbs through N1’ and S atoms on the metallic surfaces. The faradaic processes of TFF have been monitored through the SERS and UV-visible absorption spectroscopies. The SERS spectra at -1,4 V (Ag/AgCl) suggest aminomethylferrocene as one of the reduction products of TFF. By using the UV-visible absorption technique, it has been verified, at this potential, a new band at 240 nm in the spectrum, which indicates the presence of thiourea. The observation of these two reduction products has confirmed that the general reduction mechanism for thiosemicarbazonas works for TFF. Neither SERS nor UV-vis spectral changes have been observed during the redox process of FeII/FeIII (E1/2= 0,55 V). The adsorption and faradaic processes of thisemicarbazide (TSC) at silver electrode have also been studied by SERS technique. It has been verified that, in acidic and neutral media, the TSC is adsorbed through a cis-configuration at a potential close to 0,0 V, showing an interaction of the S atom through bond formation with the surface and through the H atoms bonded to N1 via ion pair formation with the adsorbed Cl- anions. At more negative potentials, the chloride anions leave the electrode surface and the TSC changes to trans-configuration. No faradaic process has been observed as reported in the literature. This result has been confirmed by using the capillary electrophoresis technique. The resonance Raman effect of the TFF has been studied, and the excitation profiles of the bands have been shown as minimum, which indicates an electronic interaction between the two cromophores of the TFF (thiosemicarbazone and ferrocenyl). The theoretic excitation profiles have been calculated by using the transform method, and the results of the obtained adjustment has indicated that there has been a distortion of the ferrocenyl vibrational modes for an electronic transition at 312 nm, assigned to the n-p* of thiosemicarbazone moiety. This result has indicated a great interaction between the two cromophores of TFF. In order to compare the resonance Raman behavior of the TFF with that of the ferrocene, the resonance Raman spectra of the ferrocene have been obtained. It has been verified that the two compounds present an anti-resonant Raman effect, even though the bands have presented very different excitation profiles from those observed in the TFF, which indicates that the incorporation of the thiosemicarbazone group into the ciclopentadienyl has changed the electronic structure of the ferrocenyl group.

A cristalografia por difração de raios X (DRX) é uma ciência eminentemente interdisciplinar, cujo desenvolvimento tem possibilitado o avanço de várias outras áreas científicas. A determinação das estruturas tridimensionais de substâncias, sejam elas naturais ou sintéticas, tem sido fundamental para o estudo e compreensão das relações entre propriedades físicas, químicas e terapêuticas, e a estrutura a nível atômico. Neste trabalho serão apresentados alguns aspectos teóricos sobre complexos ferrocenos e a teoria envolvida na determinação de estruturas cristalinas e moleculares por DRX, bem como a resolução e caracterização de dois complexos ferrocenos. Os resultados obtidos foram comparados com estruturas similares encontradas no Cambridge Structural Database. Nos compostos estudados no presente trabalho, 1,1\'- bis(difenilfosfina)ferroceno e oCHCl3, o Fe apresentou-se complexado a dois anéis de ciclopentadienila, em conformação estrela, os quais estão dispostos de forma equidistante do átomo de Fe, não apresentando distorções significativas. Devido à alta toxicidade da cis-platina no tratamento de neoplasias, muitos grupos de pesquisa têm dedicado seus esforços a encontrar fármacos análogos compatíveis, sendo os derivados de paládio muito visados por terem propriedades eletrônicas e estruturais semelhantes. Sabe-se que a geometria em torno do átomo de platina, na cis-Pt, é quadrado planar, como no presente caso, o que torna o composto oCHCl3 passível de ser estudado quanto à sua possível atividade. Uma das grandes incógnitas dentro da área de farmacologia é saber exatamente quais são os produtos oriundos da degradação de um determinado fármaco e através da determinação por DRX das estruturas cristalinas e moleculares dos dois compostos estudados, concluiu-se que os mesmos são oriundos da degradação do composto [Pd2(C2, N-(dmpa) 2 (μ-dppf)Cl2], uma vez que os compostos estudados tiveram suas estruturas determinadas a partir de um tubo contendo o composto inicial. Portanto, o presente trabalho possui uma considerável importância no estudo deste fármaco o qual pode ser usado no combate ao câncer. / X-ray diffraction is a highly interdisciplinary science, whose development has enabled the advancement of several other scientific areas. The determination of three-dimensional structures of substances, whether natural or synthetic, have been fundamental to the study and understanding of the relationships between physical, chemical, therapeutic and structure at the atomic level. This work will present some theoretical aspects of ferrocene complexes and the theory involved in determining of molecular and crystal structures by XRD, as well as resolution and characterization of two ferrocene complexes. The results were compared with similar structures found in the Cambridge Structural Database. At the compounds studied in the present work, 1,1\'-bis(diphenylphosphine)ferrocene e {(Dichloride)[bis (diphenylphosphine)-ferrocene]Palladium(II)}oCHCl3, the Fe complexes with two cyclopentadyenil rings, at star conformation, which are disposed equidistant from Fe atom, without significant distortions. Due to the elevated toxicity of cis-platine at neoplasms, many research groups have been dedicated efforts to found compatible analog drugs, which the palladium derivatives are the most researched, because of their electronic and structural properties. It has been known that the geometry around the Pt is square planar, as like as the present case, which makes the {(Dichloride)[bis (diphenylphosphine)-ferrocene] Palladium(II)}oCHCl3, possible to be study at his possibly activity. One of the great unknowns in the area of pharmacology is to know exactly which are the products of degradation of a certain drug and determining by XRD the crystal and molecular structures of both studied compounds, concluded that they are derived from the degradation of the compound [Pd2(C2, N-(dmpa) 2 (μ-dppf)Cl2], since such compounds has their structures determined from a tube containing the [Pd2(C2, N-(dmpa) 2 (μ-dppf)Cl2]. So, the present work has considerable importance in the study of this drug which can be used against cancer.

Thesis (M.Sc. (Chemistry)) -- University of Limpopo, 2020 / In an attempt to synthesise quinoxaline-ferrocene compounds with antimycobacterial activity; a series of quinoxaline alkynyl derivatives were successfully synthesised from 3- (quinoxalin-3-yl)prop-2-yn-1-ol 86A and 3-(6-chloroquinoxalin-2-yl)prop-2-yn-1-ol 86B. In this series compounds 87A – B, 90A – B, and 93A – C were intermediates obtained in an effort to synthesise quinoxaline-ferrocene compounds. Treatment of either 86A or 86B with various acid chlorides afforded quinoxaline alkynyl ester derivatives 97A - 97B. Within this series, two quinoxaline-ferrocene compounds 3-(quinoxalin-3-yl)prop-2-ynyl ferrocetate 97A-iv and 3-(6-chloroquinoxalin-2-yl)prop-2-ynyl ferrocetate 97B-iv were successfully incorporated with ferrocenoyl chloride and obtained in 42 - 43% yield. The reactions of 3-chloroquinoxaline-2-carbonyl chloride 99 with ferrocenyl alcohol and ferrocenyl amine were unsuccessful. However, 3-chloroquinoxaline-2-carbonyl ester 100A - C and amide 101A - D derivatives with various alcohols and amines were obtained. The structures of all the compounds were confirmed by spectroscopic analysis (NMR, FT-IR and HRMS). The synthesised compounds were all evaluated for preliminary in-vitro antimycobacterial activity. The results obtained exhibited compound 90B with the highest activity against Mtb H37RV strain at MIC90 of 1.13 µM, followed by 90A and 87A exhibiting MIC90 of 4.55 and 6.47 µM, respectively. The quinoxaline alkynyl ester derivatives were found to exhibit poor to good activity. Within this series, three compounds were found to exhibit antimycobacterial activity at MIC90 ˂ 20 µM with compound 97A-ii showing the highest activity at MIC90 of 16.18 µM, followed by 97A-i and 97B-iii showing MIC90 of 18.05 and 19.36 µM, respectively. From the two quixonaline-ferrocene compounds, compound 97A iv was found to exhibit antimycobacterial activity at MIC90 of 39.90 µM. However, compound 97B-iv was found to be inactive. The 3-chloroquinoxaline-2-carbonyl ester 100A - C and amide 101A - D derivatives were found to be inactive. However, compound 99-C was found to exhibit antimycobacterial activity at MIC90 of 40.66 µM. Compounds 86A, 86C, 87A and 90A were evaluated for in-vitro antiproliferative activity against cancer cell lines. The results of antiproliferative activity showed that compounds 86A and 87A exhibited excellent activity against A549 lung cancer cell lines. Compound 87A was found to be the most active against A549 cell line showing 50% viability-inhibition at 25 µM / National Research Foundation (NRF)

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第17886号 / 工博第3795号 / 新制||工||1580(附属図書館) / 30706 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 杉村 博之, 教授 酒井 明, 教授 邑瀬 邦明 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

No description available.