No description available.

No description available.

No description available.

The stereochemical course of the Pd–catalyzed Suzuki-Miyaura cross-coupling of α-substituted, enantioenriched allylic boronic esters with phenyl iodide has been examined. The secondary boronic esters were prepared in both racemic and enantioenriched forms via borylationof a lithiated carbenoid with a geometrically defined vinyl boronic ester. The geometric purities were determined to be >99% and the enantiomeric excesses of stereodefined secondary boronic esters were found to exceed 98:2. In total, 8 allylic boronic esters were successfully cross-coupled, providing arylated products with high regioselectivities (>90:10) and complete enantiospecificities (>99%). The cross-coupling of a sterically and electronically unbiased, deuterated substrate confirmed that fully equilibrated π-allylic intermediates are not involved. Additionally, correlating the absolute configurations of the allylic boronic ester and the cross-coupling product allowed us to confirm that the transmetalation step of the reaction proceeded through a closed transition state via a syn-SE’ mechanism, which further suggests the importance of the distinct Pd-O-B bond linkage. Further, the cross-coupling of vinyl iodides to secondary boronic esters was investigated. / Thesis (Master, Chemistry) -- Queen's University, 2013-11-12 19:05:19.488

Little attention has been given to the formation of the putative PdL2 species required for Pd-catalyzed cross-coupling reactions. Active species are generally difficult to store due to air-sensitivity and are therefore formed in situ at unknown rates and in unknown yields via a variety of palladium precatalysts. Commonly employed Pd(0) and Pd(II) precatalysts are often relatively ineffective because they generate only low concentrations of the bis(phosphine) species PdL2 under most reaction conditions. This thesis describes the use of the easily synthesized and easily handled Pd(η3-1-Ph-C3H4)(η5-C5H5) (I) as a superior precursor than any other documented system for the in situ formation of PdL2. Rapid and quantitative formation of active catalyst solutions allow us to demonstrate that I is also the best precatalyst known for PdL2-catalyzed crosscoupling reactions. We discuss the Suzuki-Miyaura reaction of 4-bromoanisole with phenylboronic acid and demonstrate that, under mild reaction conditions, higher initial rates and higher conversions with I can be obtained compared with other common precatalysts (Pd(OAc)2, Pd(PPh3)4, Pd2dba3, etc.) containing a variety of phosphine ligands. This methodology has also been extended to other cross-coupling reactions, as we demonstrate that higher initial rates and higher conversions with I can be obtained for a variety of Mizoroki-Heck arylations and Buchwald-Hartwig aminations. / Thesis (Ph.D, Chemistry) -- Queen's University, 2013-06-25 11:53:06.75

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This thesis is a partial investigation of instabilities in the interstellar gas which are driven by a coupling between the ambient radiation field and the gas, and which do not arise when this coupling is missed out. The modes of couplings considered are, firstly, the attenuation of the radiation with the concomitant effects on the temperature, density and composition of the gas, in various combinations. Secondly, velocity dependent effects are examined in various circumstances and thirdly, radiation pressure, not included in the other two, is looked at in the simple case in which temperature and compositional changes are excluded. The explanation of why these instabilities may be of interest, and an outline of the extent to which similar instabilities have been investigated, is given in Chapter 1. Chapter 2 gives details of the basic equations used in the case in which the absorption line shape is ignored. Many of the equations are used in the other chapters. The equations are linearised in perturbations of the density, temperature, radiation field and composition, and the resulting dispersion relationship is found for a harmonic perturbation. Because of the attenuation term in the radiative transfer equation, the polynomial has complex coefficients. In Chapter 3 we investigate the properties of the roots of a complex polynomial by an extension of Routh's methods, and derive a set of criteria to determine the number of roots which have positive real part. These roots correspond to exponentially growing perturbations, or, in other words, they correspond to instabilities. Later in the chapter we apply these methods to Field's dispersion relationship for thermal instabilities and derive many of his conclusions in a fairly simple way. By a slight extension the method yields estimates of the growth times of the instabilities. Some related situations are also examined in a similar way. After the detour of Chapter 3, Chapter 4 gives details of some models of the heating and cooling of the interstellar gas as well as of the reactions to be considered, namely the formation and destruction of H₂ and of carbon ions. Some of the limitations of the models are also discussed and the roots of the dispersion relation are given for different values of the parameters. New instabilities do appear; for H₂ their timescales of growth are rather too long to be of interest; for carbon no short timescale instabilities are discovered. Chapter 5 gives similar details for a system of pure hydrogen gas which may be of interest in studies of the formation of the first generation of stars. In Chapter 6 there is a criticism of an earlier work by Schatzman on a similar subject, in which it is shown that his analysis was wrong. Chapter 7 deals with a new possibility, namely that, as the gas moves, photons will be seen to be shifted in frequency and so the molecules will be exposed to a new set of destructive photons at frequencies which have not been selectively absorbed in the unperturbed gas. First the simplest case, that in which the temperature is unperturbed, is treated analytically. The attenuation of the radiation field is not considered. The effectiveness of this doppler-induced effect depends upon both the absorption profile and the radiation spectrum; these factors as well as temperature perturbations are included next. Both line absorption and continuum absorption are considered. The former is used to investigate the stability of the interstellar gas and of pure hydrogen gas, where hydrogen molecules are dissociated by line absorption; the latter is used in connection with HII regions and also the interstellar gas where the photodissociated species are hydrogen atoms and neutral carbon respectively. Radiation pressure was not included in the previous chapters but in Chapter 8 a modified version of Field's theory of instabilities driven by radiation pressure is presented. The new feature is that the frequency dependence of the absorption coefficient is included in the equations and this, in the case of a flat radiation spectrum, leads to an exact cancellation of the dominant term in Field's equation. Several restrictive features of Field's conclusions are thus modified and seem to make this instability rather more useful in the study of instabilities in the interstellar gas than it appeared in Field's work.

The purpose of this study was to investigate some theoretical approaches to the scattering of positive k-mesons by nucleons in an attempt to explain the experimental data. In this work the problem has been investigated by the technique of the weak coupling approximation.

Due to its unique properties and high surface area, Graphene has become a good candidate as an effective solid support for metal catalysts. The Nobel Prize in Physics for 2010 was awarded to Andre Geim and Konstantin Novoselov "for groundbreaking experiments regarding the two-dimensional material graphene". Microwave-assisted synthesis of various metallic nanostructured materials was investigated for CO oxidation applications. These metallic nanostructured materials were used to convert CO to CO2 as an effective approach for carbon monoxide elimination due to its harmful effect on health and environment. In particular, this dissertation is focusing on palladium as a transition metal that has a unique ability to activate various organic compounds to form new bonds. The prepared graphene-supported metallic nanostructured materials were successfully used to investigate Suzuki cross-coupling reaction as an important reaction in the field of pharmaceutical applications. In this research, nanostructured materials were used as solid support catalysts which showed remarkable improvements in the aspects of size, surface structure, catalytic selectivity, shape and recyclability. The nano porous structure and superparamagnetic behavior of (Fe3O4) nano particles that were used as an effective ingredient in graphene-supported palladium catalyst improved the catalytic activity and the catalyst recyclability simply by using an external magnetic field. This research has been divided into two main categories; the first category is to investigate other metal oxides as a solid support for palladium to be used in CO oxidation catalysis. The second category will focus on improving of solid support systems of palladium – magnetite catalyst to increase recyclability. The final stage of this investigation will study the use of these solid supported metal catalysts in continuous heterogeneous processes under flow reaction conditions. The structural, morphological and physical properties of graphene-based nanocomposites described herein were studied using standard characterization tools such as TEM, SEM, X-ray diffraction, XPS and Raman spectroscopy.

N-Heterocyclic carbenes (NHCs) have emerged as appropriate replacements for phosphines in transition metal catalyzed cross-coupling chemistry. The advantages of NHCs over phosphines include ease of handling, minimal toxicity, stability and powerful electron donating properties. Improvement of catalytic processes has become increasingly relevant in light of prospective applications of organic transformations in industry as well as in synthetic laboratories. To that end, NHCs represent an important class of catalysts and catalyst modifiers which mandate continued research efforts. Prospective applications of processes catalyzed by NHCs and NHC-metal catalysts provide a strong impetus to develop them and related methodologies. This dissertation focuses on the development of NHCs and NHC ligated metal complexes in various catalytic transformations. NHC ligated palladium catalysts were synthesized in simplified protocols amenable to large-scale industrial applications. The catalysts were utilized in developing different valuable coupling methodologies. Significant advances were achieved in Suzuki-Miyaura, á-arylation of ketones and Kumada-Tamao-Corriu cross coupling reactions. The focus of the work was to make the synthesized catalysts and their activity in these methodologies acceptable to wider range of applications. The strongly nucleophilic nature and easily tunable steric and electronic properties of NHCs have been exploited to mediate organic transformations by utilizing NHCs as catalysts. The metal-free catalysis has an added advantage of being more environmentally friendly. NHCs have proven to be excellent transesterification catalysts for reactions of alcohol and esters. An efficient catalytic system, widening the scope of N-heterocyclic carbenes catalyzed transesterification/acylation reaction of alcohols is described. The methodology has been expanded to include secondary alcohols as well as phosphorus based esters.