Z-selective olefin metathesis using chelating ruthenium alkylidene catalysts

Publications about olefin metathesis will generally discuss how the discovery and development of well-defined catalysts to carry out this unique transformation have revolutionized many fields, from natural product and materials chemistry, to green chemistry and biology. However, until recently, an entire manifestation of this methodology had been inaccessible. Except for a few select examples, metathesis catalysts favor the thermodynamic trans- or E-olefin products in cross metathesis (CM), macrocyclic ring closing metathesis (mRCM), ring opening metathesis polymerization (ROMP), and many other types of reactions. Judicious choice of substrates had allowed for the direct synthesis of cis- or Z-olefins or species that could be converted upon further reaction, however the catalyst controlled synthesis of Z-olefins was not possible until very recently.

Research into the structure and stability of metallacyclobutane intermediates has led to the proposal of models to impart Z-selectivity in metathesis reactions. Having the ability to influence the orientation of metallacyclobutane substituents to cause productive formation of Z- double bonds using steric and electronic effects was highly desired. The first successful realization of this concept was by Schrock and Hoveyda et al. who synthesized monoaryloxide pyrolidine (MAP) complexes of tungsten and molybdenum that promoted Z-selective CM. The Z-selectivity of these catalysts was attributed to the difference in the size of the two axial ligands. This size difference influences the orientation of the substituents on the forming/incipient metallacyclobutane intermediate to a cis-geometry and leads to productive formation of Z-olefins. These catalysts have shown great utility in the synthesis of complicated natural product precursors and stereoregular polymers. More recently, ruthenium catalysts capable of promoting Z-selective metathesis have been reported by our group and others. This thesis will discuss the development of ruthenium-based NHC chelated Z-selective catalysts, studies probing their unique metathesis mechanism, and synthetic applications that have been investigated thus far.

Chapter 1 will focus on studies into the stability of NHC chelated complexes and the synthesis of new and improved stable chelating architectures. Chapter 2 will discuss applications of the highly active and Z-selective developed in Chapter 1, including the formation of lepidopteran female sex pheromones using olefin cross metathesis and highly Z- and highly E-macrocycles using macrocyclic ring closing metathesis and Z-selective ethenolysis. Chapter 3 will explore studies into the unique mechanism of olefin metathesis reactions catalyzed by these NHC chelated, highly Z-selective catalysts, explaining observed trends by investigating the stability of relevant, substituted metallacyclobutane intermediates.

Electrocatalytic activity of transition metal substituted heteropolytungstates

The electrochemical and electrocatalytic behavior of a series of heteropolytungstate anions in which a tungsten atom in the well known Keggin structure has been replaced by an iron atom is described. All of the iron substituted ions exhibit a one electron reversible couple associated with the Fe³⁺ center and a pair of two electron waves attributed to electron addition and removal from the tungsten oxo framework. The pH and ionic strength effects upon the various electrochemical processes are discussed and interpreted in terms of a competition between protonation and ion pairing of the highly negatively charged ions.

The anions are efficient catalysts for the electroreduction of hydrogen peroxide. A catalytic mechanism involving a formally Fe(IV) intermediate is proposed. Pulse radiolysis experiments were employed to detect the intermediate and evaluate the rate constants for the reactions in which it is formed and decomposed. A chain mechanism for the catalytic decomposition of hydrogen peroxide in which the Fe center shuttles between the +2, +3, and +4 oxidation states is proposed to explain the non-integral stoichiometry observed for the iron substituted polytungstate catalyzed electroreduction of hydrogen peroxide.

The anions are also efficient electrocatalyst for the electrochemical conversion of nitric oxide to ammonia. The catalyzed reduction does not produce hydroxylamine as an intermediate and appears to depend upon the ability of the multiply reduced heteropolytungstates to deliver several electrons to the bound NO group in a concerted step. A valuable feature of the heteropolytungstates is the ease at which the formal potentials of the several redox couples they exhibit may be shifted by changing the identity of the central heteroatom. Exploitation of this feature provided diagnostic information that was decisive in establishing the mechanism of electrocatalytic reduction.

The iron substituted heteropolytungstates are not degraded by repeated cycling between their oxidized and reduced states. They also show superior activity compared to their unsubstituted analogues, indicating that the Fe center acts as a binding site that facilitates inner-sphere electron transfer processes. The basic electrochemistry of several other transition metal substituted Keggin ions is also described.

Trimethylsilyl anions: stereospecific deoxygenation of epoxides and trimethylsilyldehalogenation of aryl halides

I. Trimethylsilylpotassium reacts with epoxides to give olefins with inversion of stereochemistry. The reaction appears to proceed via the potassium β-silyl alkoxide (2) formed from the S_N2 attack of the silyl anion on the epoxide. Subsequent stereospecific synelimination of 2 affords the olefin of inverted stereo-chemistry. The reaction is convenient and preparatively useful.

The byproduct of the reaction, potassium trimethylsilanolate (17), effectively cleaves hexamethyldisilane to yield trimethylsilylpotassium. Since the latter reagent is generated and reacted in situ with epoxides, the overall reaction can be carried out with less than one equivalent of potassium methoxide.

II. The reaction of aryl halides with trimethylsilyl anions in HMPT provides good yields of aryltrimethylsilanes, useful synthetic intermediates. The choice of metal cation is unimportant. Chlorides and bromides give high yields of silylated products, while iodides give lower yields, with correspondingly increased amounts of reduced products. Arylammonium and arylphosphonium salts also undergo the reaction.

We have permissive evidence for the reaction proceeding via both aryl radical and aryl anion intermediates.

III. Trimethylsilyl and trimethylstannyl methoxycarbene complexes of chromium and tungsten have been prepared. One of these, (CO)_5WC(OMe)SnMe_3, reacts with norbornene at 80° to afford a new olefin polymer. Efforts to effect the alpha-elimination of the nonmetallic carbene ligands have not yet been successful. Reactions of these carbene complexes with acetone have been investigated.

Nuclear hyperfine interactions in W^(182), W^(183), and Pt^(195) as studies by the Mossbauer effect

The Mössbauer technique has been used to study the nuclear hyperfine interactions and lifetimes in W¹⁸² (2⁺ state) and W¹⁸³ (3/2^- and 5/2^- states) with the following results: g(5/2^-)/g(2⁺) = 1.40 ± 0.04; g(3/2^- = -0.07 ± 0.07; Q(5/2^-)/Q(2⁺) = 0.94 ± 0.04; T_1/2(3/2^-) = 0.184 ± 0.005 nsec; T_1/2(5/2^-) >̰ 0.7 nsec. These quantities are discussed in terms of a rotation-particle interaction in W¹⁸³ due to Coriolis coupling. From the measured quantities and additional information on γ-ray transition intensities magnetic single-particle matrix elements are derived. It is inferred from these that the two effective g-factors, resulting from the Nilsson-model calculation of the single-particle matrix elements for the spin operators ŝ_z and ŝ₊, are not equal, consistent with a proposal of Bochnacki and Ogaza.

The internal magnetic fields at the tungsten nucleus were determined for substitutional solid solutions of tungsten in iron, cobalt, and nickel. With g(2⁺) = 0.24 the results are: |H_eff(W-Fe)| = 715 ± 10 kG; |H_eff(W-Co)| = 360 ± 10 kG; |H_eff(W-Ni)| = 90 ± 25 kG. The electric field gradients at the tungsten nucleus were determined for WS₂ and WO₃. With Q(2⁺) = -1.81b the results are: for WS₂, eq = -(1.86 ± 0.05) 10¹⁸ V/cm²; for WO₃, eq = (1.54 ± 0.04) 10¹⁸ V/cm² and ƞ = 0.63 ± 0.02.

The 5/2^- state of Pt¹⁹⁵ has also been studied with the Mössbauer technique, and the g-factor of this state has been determined to be -0.41 ± 0.03. The following magnetic fields at the Pt nucleus were found: in an Fe lattice, 1.19 ± 0.04 MG; in a Co lattice, 0.86 ± 0.03 MG; and in a Ni lattice, 0.36 ± 0.04 MG. Isomeric shifts have been detected in a number of compounds and alloys and have been interpreted to imply that the mean square radius of the Pt¹⁹⁵ nucleus in the first-excited state is smaller than in the ground state.

Metallogenic Provinces of the Southwestern United States and Northern Mexico

Some of the metallogenic provinces of the southwestern United States and northern Mexico are defined by the geographic distribution of trace elements in the primary sulfide minerals chalcopyrite and sphalerite. The elements investigated include antimony, arsenic, bismuth, cadmium, cobalt, gallium, germanium, indium, manganese, molybdenum, nickel, silver, tellurium, thallium, and tin. Of these elements, cobalt, gallium, germanium, indium, nickel, silver, and tin exhibit the best defined geographic distribution.

The data indicate that chalcopyrite is the preferred host for tin and perhaps molybdenum; sphalerite is the preferred host for cadmium, gallium, germanium, indium, and manganese; galena is the preferred host for antimony, bismuth, silver, tellurium, and thallium; and pyrite is the preferred host for cobalt, nickel, and perhaps arsenic. With respect to the two minerals chalcopyrite and sphalerite, antimony, arsenic, molybdenum, nickel, silver, and tin prefer chalcopyrite; and bismuth, cadmium, cobalt, gallium, germanium, indium, manganese, and thallium prefer sphalerite. This distribution probably is the result of the interaction of several factors, among which are these: the various radii of the elements, the association due to chemical similarities of the major and trace elements, and the degree of ionic versus covalent and metallic character of the metal-sulfur bonds in chalcopyrite and sphalerite. The type of deposit, according to a temperature classification, appears to be of minor importance in determining the trace element content of chalcopyrite and sphalerite.

A preliminary investigation of large single crystals of sphalerite and chalcopyrite indicates that the distribution within a single crystal of some elements such as cadmium in sphalerite and indium and silver in chalcopyrite is relatively uniform, whereas the distribution of some other elements such as cobalt and manganese in sphalerite is somewhat less uniform and the distribution of tin in sphalerite is extremely erratic. The variations in trace element content probably are due largely to variations in the composition of the fluids during the growth of the crystals, but the erratic behavior of tin in sphalerite perhaps is related to the presence of numerous cavities and inclusions in the crystal studied.

Maps of the geographic distribution of trace elements in chalcopyrite and sphalerite exhibit three main belts of greater than average trace element content, which are called the Eastern, Central, and Western belts. These belts are consistent in trend and position with a beltlike distribution of copper, gold, lead, zinc, silver, and tungsten deposits and with most of the major tectonic features. However, there appear to be no definite time relationships, for as many as four metallogenic epochs, from Precambrian to late Tertiary, are represented by ore deposits within the Central belt.

The evidence suggests that the beltlike features have a deep seated origin, perhaps in the sub-crust or outer parts of the mantle, and that the deposits within each belt might be genetically related through a beltlike compositional heterogeneity in the source regions of the ores. Hence, the belts are regarded as metallogenic provinces.

CE3+对ER3+/Yb3+共掺TeO2-WO3-ZnO玻璃发光性能的影响

Ce3+ ions were introduced into the Er3+/Yb3+ -codoped TeO2-WO3-ZnO glasses, and the effect of Ce3+ on the emission properties at 1.5 mu m band and the upconversion luminescence of Er3+ in the glasses was investigated. With the increasing of Ce3+ concentration, the emission intensity of Er3+ at 1.5 mu m band increases firstly, and then decreases. The optimal doping concentration of Ce3+ is about 2.07 x 10(20)/cm(3). As for the Er3+ emission at 1.5-mu m band, the fluorescence lifetime decreases a little from 3.4ms to 3.0ms, while the full width at half maximum (FWHM) hardly changes with the increase of Cc 3+ concentration. Due to the effective cross relaxation between Ce3+ and Er3+ : Er3+ (I-4(11/2)) + Ce3+ (F-2(5/2)) -> Er3+ (I-4(13/2)) + Ce3+ (F-2(7/2)), the upconversion emission intensity of Er3+ is reduced greatly. But when Ce3+ -doping concentration is too high, the other cross relaxation between Ce3+ and Er3+ : Er3+ (4I(13/2)) + Ce3+ (F-2(5/2)) -> Er3+ (I-4(15/2)) + Ce3+ (F-2(7/2)) happens, which depopulates the I-4(13/2) level of Er3+ and results in the decrease of the emission intensity and fluorescence lifetime of Er3+ at 1.5 mu m band.

掺铒碲-钨-钠玻璃基质的光谱性质研究

制备了用于离子交换法制备光波导器件的掺铒碲-钨-钠玻璃基质。应用扎得-奥菲而特(Judd—Ofelt)理论计算了玻璃样品的三个强度参量，由强度参量计算了Er^3+离子的自发跃迁几率、荧光分支比等光谱参量；应用麦克库玻(McCumber)理论，计算了Er^3+离子在1．5μm的受激发射截面，荧光测试发现Er^3+离子的荧光半峰全宽可达65nm。比较了Er^3+离子在不同玻璃基质中的光谱特性。结果表明，Er^3+离子在碲-钨-钠玻璃中具有较高的受激发射截面和较宽的荧光半峰全宽，可以用于宽带光波导器件的制备。

掺铒碲钨酸盐玻璃及其平面波导

研制了一种用于宽带波导放大器的掺铒碲钨酸盐激光玻璃材料，对玻璃热稳定性、光谱性质进行了表征，并在其上采用离子交换法制作了平面光波导．掺铒碲钨酸盐玻璃的转变温度Tg和析品开始温度Tx分别为377．1和488．5℃；荧光半高宽为52nm；应用McCumber理论，计算得出Er^3+离子4I13／2→^4I15／2跃迁在峰值波长1532nm的受激发射截面为0．91×10^-20cm^2．不同条件下制作了在632．8nm处多模的平面光波导，通过拟合得到Ag^+离子在300℃的有效扩散系数De为2．82×10^-1

Helmholtz Fermi surface harmonics: an efficient approach for treating anisotropic problems involving Fermi surface integrals

We present a new efficient numerical approach for representing anisotropic physical quantities and/or matrix elements defined on the Fermi surface (FS) of metallic materials. The method introduces a set of numerically calculated generalized orthonormal functions which are the solutions of the Helmholtz equation defined on the FS. Noteworthy, many properties of our proposed basis set are also shared by the FS harmonics introduced by Philip B Allen (1976 Phys. Rev. B 13 1416), proposed to be constructed as polynomials of the cartesian components of the electronic velocity. The main motivation of both approaches is identical, to handle anisotropic problems efficiently. However, in our approach the basis set is defined as the eigenfunctions of a differential operator and several desirable properties are introduced by construction. The method is demonstrated to be very robust in handling problems with any crystal structure or topology of the FS, and the periodicity of the reciprocal space is treated as a boundary condition for our Helmholtz equation. We illustrate the method by analysing the free-electron-like lithium (Li), sodium (Na), copper (Cu), lead (Pb), tungsten (W) and magnesium diboride (MgB2)

Fluorescence lifetime increase by introduction of F- ions in ytterbium-doped TeO2-based glasses

this paper was retracted

Identification of treatments targeting PMLexpressing breast cancers

The main aim of this project is to find a suitable ATO concentration to combine with already approved chemotherapeutic agents to find that synergistic effect in triple negative breast cancer MDA-MB 231 cell line, as a new strategy to treat the disease.

Avaliação da microestrutura, microdureza e resistência à corrosão de juntas soldadas de uma liga de Ni-Cr obtidas através de diferentes processos de soldagem

Este trabalho avaliou o comportamento eletroquímico do metal de base (MB) de uma liga a base de níquel-cromo em relação a juntas soldadas desta liga obtidas pelos processos de brasagem (BRA) e Tungsten Inert Gas (TIG), imersos em saliva artificial com pH 2,5 e 5,5. Foram também realizados ensaios de microdureza e caracterização microestrutural, por meio de microscopia óptica e eletrônica de varredura e análise química semi-quantitativa por EDS, nos grupos MB, TIG, BRA e no cordão de solda a laser (LAS). O MB apresentou uma matriz rica em níquel e cromo, distribuída em um arranjo dendrítico típico, apresentando inclusões metálicas de silício e titânio, além de porosidades. As soldas TIG e LAS revelaram uma microestrutura mais refinada que o MB, mostrando, entretanto, uma mesma composição química e distribuição de seus elementos. A solda BRA apresentou diferenças marcantes em sua microestrutura, composição química e distribuição de seus elementos em relação ao MB. Os dados de microdureza Vickers (HV), potencial de corrosão (Ecorr) e densidade de corrente de corrosão (jcorr) foram analisados com ANOVA e teste de Tukey (p<0,05). Para determinação da influência do pH quanto a resistência à corrosão dos grupos MB, TIG e BRA, empregou-se o teste t de Student (p<0,05). O MB apresentou menor média de microdureza (256,13 9,39 HV), seguido pelos grupos TIG (271,53 8,07 HV), LAS (303,73 13,93 HV) e BRA (551,99 37,73 HV). Em pH 2,5 as médias do Ecorr (mV) para o MB, TIG e BRA foram, respectivamente, -67,9 8,43, -52,78 16,74, e -284,33 19,04; e em pH 5,5, médias de -54,03 21,15, -62,08 20,16 e -278,8 28,96. Os valores médios de jcorr (A.cm-2) para o MB, TIG e BRA em pH 2,5 foram, respectivamente, 2,49 0,95, 5,584 1,64 e 27,45 4,9; e em pH 5,5, médias de 1,929 0,83, 4,267 1,51 e 54,2 11,96. Os grupos MB e TIG apresentaram boa resistência à corrosão, com maior módulo de impedância em relação ao grupo BRA. As diferenças no pH da saliva artificial não alteraram o comportamento corrosivo dos grupos MB e TIG. Entretanto, observou-se uma redução marcante na jcorr e no módulo de impedância nas soldas obtidas pelo processo de brasagem. O grupo BRA apresentou corrosão galvânica ao ser analisado formando par com o MB, mostrando uma jcorr de 5,3 A.cm-2. Entretanto, o mesmo não foi observado quando o MB foi associado à solda TIG, onde a jcorr foi cerca de 150 vezes menor. O grupo BRA, além de apresentar um comportamento eletroquímico muito diferente do MB, revelou diferenças marcantes quanto a composição química, aspecto microestrutural e microdureza. As juntas TIG e LAS mostraram semelhanças químicas e microestruturais em relação ao MB, sendo que na solda TIG esta semelhança foi ainda mais evidente. Além disto, a solda TIG apresentou um comportamento eletroquímico muito semelhante ao MB e, portanto, parecendo ser mais recomendável para soldar ligas odontológicas de níquel-cromo em relação aos demais processos de soldagem aqui avaliados.

Metalogenia em terrenos de alto grau metamórfico: as mineralizações tungstaníferas da área de Monumento/Cacaria RJ

Em trabalho de prospecção geoquímica regional por concentrado de bateia (PEREIRA e SANTOS, 1983) foi evidenciado na região de Cacaria, município de Piraí, ocorrências de scheelita. Com o objetivo de investigar a possível fonte litológica desta ocorrência, foram realizadas amostragens de sedimentos de corrente e concentrado de bateia além de investigações de campo para sua fonte. Elaborouse ainda um mapa geológico em escala de detalhe 1:25.000. As unidades estratigráficas base utilizadas no mapa foram definidas em trabalhos da empresa RIOFINEX (1977) durante pesquisas para mineralizações de Pb-Zn na região de Rio Claro. Ensaios laboratoriais envolvendo descrição de lâminas petrográficas, difratometria de raios X, fluorescência de raios X, espectrometria Raman, microscopia eletrônica de varredura e o auxílio do mineralight de ondas curtas. As mineralizações scheelitíferas encontradas foram classificadas segundo um modelo do tipo sedimentar exalativo, localmente com possíveis contribuições de atividades metassomáticas tardias, concentrando a mineralização, assim como proposto para algumas ocorrências já descritas no nordeste brasileiro.

Post-CMOS wafer level growth of carbon nanotubes for low-cost microsensors--a proof of concept.

Here we demonstrate a novel technique to grow carbon nanotubes (CNTs) on addressable localized areas, at wafer level, on a fully processed CMOS substrate. The CNTs were grown using tungsten micro-heaters (local growth technique) at elevated temperature on wafer scale by connecting adjacent micro-heaters through metal tracks in the scribe lane. The electrical and optical characterization show that the CNTs are identical and reproducible. We believe this wafer level integration of CNTs with CMOS circuitry enables the low-cost mass production of CNT sensors, such as chemical sensors.

On-chip deposition of carbon nanotubes using CMOS microhotplates.

The direct deposition of carbon nanotubes on CMOS microhotplates is demonstrated in this paper. Tungsten microhotplates, fabricated on thin SOI membranes aside CMOS control circuitry, are used to locally grow carbon nanotubes by chemical vapour deposition. Unlike bulk heating of the entire chip, which could cause degradation to CMOS devices and interconnects due to high growth temperatures in excess of 500 °C, this novel technique allows carbon nanotubes to be grown on-chip in localized regions. The microfabricated heaters are thermally isolated from the rest of the CMOS chip as they are on the membranes. This allows carbon nanotubes to be grown alongside CMOS circuitry on the same wafer without any external heating, thus enabling new applications (e.g. smart gas sensing) where the integration of CMOS and carbon nanotubes is required.