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Tesis sobre el tema "Inorganic chemistry"

Autor: Grafiati
Publicado: 4 de junio de 2021
Última modificación: 9 de junio de 2025

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1

Clancy, Gerald Patrick. "Synthetic inorganic chemistry : novel metallocenes and inorganic fullerenes." Thesis, University of Oxford, 2000. http://ora.ox.ac.uk/objects/uuid:9c7f7c35-bb8f-4117-8e2e-e56a9fbcbeab.

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This thesis is divided into two parts. The first part concerns the synthesis and characterisation of substituted metallocene complexes of the transition and main group metals. The second part describes the preparation and characterisation of inorganic fullerene (IF)-related materials. <strong>Chapter 1</strong> reviews the chemistry of dialkyl- and diaryl-phosphino substituted cyclopentadienyl complexes of the transition metals. <strong>Chapter 2</strong> describes the synthesis and characterisation of the new ligands [M(C<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PMe<sub>2</sub>] (M = H, Li, Na and K) via the precursors [HC<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PHMe<sub>2</sub>][X] (X = Cl and PF<sub>6</sub>). The synthesis, characterisation and chemical reactivity of the compounds [Zr{{η-C<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PMe<sub>2</sub>}<sub>2</sub>Cl<sub>2</sub> and [Mn{η-C<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PMe<sub>2</sub>}<sub>2</sub>] is reported together with supporting evidence for the synthesis of the bimetallic complex [Zr{U+03B7-C<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PMe<sub>2</sub>}<sub>2</sub>Cl<sub>2</sub>PtI<sub>2</sub>] and the complex [Mn{η-C<sub>5</sub>Me<sub>4</sub>)CH<sub>2</sub>PMe<sub>2</sub>B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>}<sub>2</sub>]. <strong>Chapter 3</strong> provides a brief introduction into the field of main group metallocenes and describes the synthesis and characterisation of the new main group metallocenes [M{η- C<sub>5</sub>H<sub>4</sub>)CMe<sub>2</sub>PMe<sub>2</sub>}<sub>2</sub>] (M = Pb and Sn). The B(C<sub>6</sub>F<sub>5</sub>)<sub>3 adduct [Pb{η-C<sub>5</sub>H<sub>4</sub>)CMe<sub>2</sub>PMe<sub>2</sub>(B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>}<sub>2</sub>] has also been synthesised. The main group - transition metal bimetallic complex [Pb{η-C<sub>5</sub>H<sub>4</sub>)CMe<sub>2</sub>PMe<sub>2</sub>}<sub>2</sub>PtI<sub>2<sub> in which the substitutedplumbocene acts as a bidentate ligand, has been characterised by mass spectrometry and <sup>31</sup>P{<sup>1</sup>H}NMR spectroscopy. <strong>Chapter 4</strong> provides an introduction into the field of IF-related materials and an overview of the analytical techniques used in their characterisation. <strong>Chapter 5</strong> describes the preparation and characterisation of IF-MoS<sub>2</sub> and IF-(Nb,W)S<sub>2</sub> materials from MoC and the binary oxides Nb<sub>8</sub> W<sub>9</sub>O<sub>47</sub> and Nb<sub>4</sub>W<sub>13</sub>O<sub>47</sub> respectively. A powder X-ray diffraction study of the conversion of WC to WO<sub>3-X</sub> and the subsequent sulfidisation by H<sub>2</sub>S to form novel IF-WS<sub>2</sub> morphologies is also described. <strong>Chapter 6</strong> describes the preparation of amorphous Group 5 metal (V, Nb and Ta) oxides using the metal vapour synthesis technique. These amorphous precursors have been annealed in a reducing atmosphere to form the oxide phases U+03B1-V<sub>2</sub>O<sub>3</sub>, NbO<sub>2</sub> and TT-Ta<sub>2</sub>O<sub>5</sub> which have been identified by powder X-ray diffraction. Upon reaction with H<sub>2</sub>S, the crystalline oxides afford layered sulfides of the form MS<sub>2</sub> (M = V, Nb and Ta), some of which exhibit behaviour typical of IF-like materials and have been characterised by HRTEM, powder X-ray diffraction and EDX analysis. Chapter 7 outlines the experimental details for the synthesis, characterisation, reactions and compounds described in the preceding chapters. <strong>Chapter 8</strong> presents the characterising data for the new compounds described in chapters 2 and 3. <strong>Appendix A</strong> contains details of the crystallographic data for the structurally characterised compound [Mn{η-C<sub>5</sub>Me<sub>4</sub>)CH<sub>PMe<sub>2</sub>}<sub>2</sub>].
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2

Hubert, Jason Dominic. "Studies in synthetic inorganic chemistry." Thesis, University of Oxford, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.334376.

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3

Bown, M. "Organoruthenaborane chemistry." Thesis, University of Leeds, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.377857.

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4

Smith, Paul David. "Arene-ruthenium chemistry." Thesis, University of Nottingham, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.357040.

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5

Grimes-Marchan, Thomas V. Cundari Thomas R. "Quantum perspectives on physical and inorganic chemistry." [Denton, Tex.] : University of North Texas, 2007. http://digital.library.unt.edu/permalink/meta-dc-5172.

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6

Suman, Priya. "The inorganic and organometallic chemistry of paracyclophanes." Thesis, Imperial College London, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.299296.

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7

Davin, Thomas J. "Computational chemistry of organometallic and inorganic species." Thesis, University of Glasgow, 2009. http://theses.gla.ac.uk/925/.

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This thesis presents computational investigations of problems related to redox processes and structural rearrangement in inorganic systems. Density functional theory has been used to gain insight into the origin and nature of such reactions. The work presented concerns two main topics: hydrogenase-like systems containing an Fe2 core and carbonphosphorus cluster compounds. In chapters II and III, we describe the impact of reduction, an important phenomenon in the H2 production catalytic cycle, on a hydrogenase-like model. In collaboration with Talarmin and co-workers who have conducted careful electrochemical studies, we have used DFT to identify structures of species observed in cyclic voltammetry. We have also studied the binding of a proton to similar systems and, through the calculation of chemical shifts and coupling constants, confirmed the structures of iron hydrides observed by 1H NMR spectroscopy. In chapter V we focus on carbon-phosphorus systems that can exist in 2 or more isomeric forms. We address first the case of a system of formula C6H4P3 which has the right valence configuration to exist either as a planar structure or as a 3-dimensional cluster (nido according to Wade’s rules). We then examine whether it is possible to control the preferred conformation by the addition of substituents on the phenyl ring. Finally, we look at the rearrangement of a planar diphosphene into a cage isomer and try to understand the mechanism and in particular the role of the protonation in the conversion from planar to 3-dimensional structure.
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8

Bihari, Shailja. "Bio-inorganic chemistry of manganese and titanium." Thesis, University of Edinburgh, 2002. http://hdl.handle.net/1842/9995.

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A wide range of metals are transported in the body by the protein transferrin, including both essential metal ions and probably also metals used in therapeutic agents. The metal binding sites on transferrin contain tyrosine, histidine and aspartate ligands. This thesis is concerned with studies of the essential metal ion manganese, and with titanium, which is used in anticancer agents. In order to aid the characterisation of Mn(III) and Ti(IV) transferrins, the Mn(III) and Ti(IV) complexes with the model ligand ethylenebis[(a-hydroxyphenyl)glycine](H₄EHPG) have been studied. The Mn(III) complexes rac-Na[Mn(EHPG)].3H₂0 (1) and rac,mesoNa[Mn(EHPG)].H₂0 (2), have been prepared and their X-ray crystal structures determined. Complex 1 contains N(S,S)C(R,R) configurations at the N and C stereogenic centres, whilst in the unit cell of complex 2 there are two independent molecules, 2a (mesa) and 2b (rac), with N(R,R)C(S,R) and N(R,R)C(S,S) configurations, respectively. Enantiomers of each complex are also present. The Mn(III) centres have Jahn-Teller-distorted octahedral geometry, with two long bonds and four short bonds. ¹H NMR spectra of these high-spin d⁴ paramagnetic complexes are reported. These complexes give rise to similar ligand (phenolate)-tometal charge-transfer bands as Mn(III)-transferrin. Dissociation of Mn(III) from EHPG occurs below pH 3.4. The Ti(IV) complex of rac-[Ti(EHPG)(H₂0)].1113H₂0 (3) has also been prepared and the X-ray crystal structure determined. All previously-reported crystalline racEHPG metal complexes contain N(S,S)C(R,R), or N(R,R)C(S,S) isomers, whereas 3 unexpectedly contains the N(S,S)C(S,S) and N(R,R)C(R,R) forms. 2D NMR studies indicate that 3 has a similar structure in solution to that in the solid state. A ligand (phenolate)-to-metal charge transfer band was observed at 386 nm, similar to that seen for Ti(IV)-transferrin. Ti(IV)EHPG was stable at pH values down to 1, however, the complex decomposed above pH 7. Mn(III)-transferrin complexes were prepared by air oxidation of Mn(II) in the presence of transferrin. The oxidation state of manganese bound to transferrin was Abstract confirmed by K edge EXAFS. Analysis of the EXAFS data revealed that the metal centre is also Jahn-Teller distorted but with four long bonds and two short bonds, i.e. an inverse distortion to that seen in the Mn(III)EHPG model complexes. Attempts to prepare other Mn(III) complexes which might be suitable for studies of Mn transfer to proteins are described and include cyclam and bicyclam as ligands. The crystal structure of [Mn(cyclam)Ch]Cl₂H₂0 was determined, and contained two long axial Mn-Cl bonds of 2.5249 Å. This complex was shown by electronic absorption spectroscopy to undergo a complicated series of reactions in aqueous solution. K edge EXAFS measurements suggested that at least one Cl ligand dissociated from the complex in aqueous solution. The hydrolysis was shown to be inhibited by the presence of fluoride.
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9

Grimes-Marchan, Thomas V. "Quantum Perspectives on Physical and Inorganic Chemistry." Thesis, University of North Texas, 2007. https://digital.library.unt.edu/ark:/67531/metadc5172/.

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Applications of computational quantum chemistry are presented, including an analysis of the photophysics of cyclic trinuclear coinage metal pyrazolates, an investigation into a potential catalytic cycle utilizing transition metal scorpionates to activate arene C-H bonds, and a presentation of the benchmarking of a new composite model chemistry (the correlation consistent composite approach, ccCA) for the prediction of classical barrier heights. Modeling the pyrazolate photophysics indicates a significant geometric distortion upon excitation and the impact of both metal identity and substituents on the pyrazolates, pointing to ways in which these systems may be used to produce rationally-tuned phosphors. Similarly, thermodynamic and structural investigations into the catalyst system points to promising candidates for clean catalytic activation of arenes. The ccCA was found to reproduce classical reaction barriers with chemical accuracy, outperforming all DFT, ab initio, and composite methods benchmarked.
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10

Wilson, David James. "Phosphaalkyne derived phosphaorganometallic chemistry." Thesis, University of Sussex, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.324141.

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11

Anderson, Kirsty Mackenzie. "Structural transition metal chemistry." Thesis, University of Bristol, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.251082.

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12

Keep, Ann Kathleen. "Ruthenium boron cluster chemistry." Thesis, University of Cambridge, 1990. https://www.repository.cam.ac.uk/handle/1810/272941.

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13

Balaraman, Lakshmi. "COORDINATION CHEMISTRY OF N,N’- AZODOXIDES." Cleveland State University / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=csu1556986156564604.

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14

Rabinovich, Daniel. "Chemistry: “Biological Inorganic Chemistry. Structure and Reactivity”, Bertini, Gray, Stiefel and Valentine." Revista de Química, 2012. http://repositorio.pucp.edu.pe/index/handle/123456789/101357.

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15

Walker, Gary Lawrence Patrick. "Studies in imido molybdenum chemistry." Thesis, Imperial College London, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.266639.

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16

Trussell, Stephen John. "Transition metal-mediated organosilicon chemistry." Thesis, Imperial College London, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.298136.

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17

Michaelidou, Despo M. "Synthetic studies in organometallic chemistry." Thesis, University of Oxford, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.358726.

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18

Speel, Robert S. "Synthetic studies in gallium chemistry." Thesis, University of Oxford, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.315771.

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19

Gardener, Martin. "Studies in sol-gel chemistry." Thesis, Nottingham Trent University, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.341276.

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20

Dost, Kenan. "Supercritical fluids in analytical chemistry." Thesis, University of Nottingham, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.324702.

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21

Richards, D. G. "Non-aqueous chemistry of polyoxometalates." Thesis, University of Newcastle Upon Tyne, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.260951.

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22

Guigley, Robert. "Chemistry of some hexanuclear complexes." Thesis, University of Sussex, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.359105.

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23

Baghurst, David Richard. "Applications of microwave techniques in synthetic inorganic chemistry." Thesis, University of Oxford, 1992. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.306688.

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24

Liu, Sophie Ph D. Massachusetts Institute of Technology. "Harnessing inorganic coordination chemistry for novel sensing applications." Thesis, Massachusetts Institute of Technology, 2016. http://hdl.handle.net/1721.1/105029.

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Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2016.<br>Cataloged from PDF version of thesis.<br>Includes bibliographical references.<br>We explore strategies to exploit the rich chemical reactivity available to inorganic coordination complexes in order to realize chemiresistive detectors, electronic device elements that undergo a change in resistance in the presence of analyte, through either incorporation of a conductive material (i.e., carbon nanotubes) or reliance on intrinsic conductivity. We seek to elucidate fundamental principles that govern these chemical detectors and use these insights to aid our design of effective chemical detection systems. In Chapter 1, we give an overview of chemiresistors in chemical detection with an emphasis on those based on carbon nanotubes. In Chapter 2, we employ metalloporphyrin complexes bearing late first-row transition metal centers in composites with single-walled carbon nanotubes (SWCNTs) in a chemiresistive sensor array capable of classifying various volatile organic compounds (VOCs) through the use of statistical analyses. In this study, we hypothesize that a swelling-based transduction mechanism is a significant contributor to the observed response. In Chapter 3, we demonstrate that the metalloporphyrin-SWCNT chemiresistor can be optimized through rational design for the detection of amines relevant to meat spoilage. Within the meso-tetraarylporphinatocobalt manifold, increasing the electron deficiency of the metal center through synthetic tuning can increase the device's sensitivity to amines, allowing for a detector to monitor the decomposition of meat. In Chapter 4, we describe the design of a sensor for carbon monoxide, fabricated from carbon nanotubes and an organocobalt(III) complex. This work represents the first example of a carbon monoxide detector based on carbon nanotubes functionalized with a molecular species. In Chapter 5, we immobilize a composite of SWCNTs and poly(4-vinylpyridine) onto glass substrates decorated with gold electrodes and then incorporate PdCl₂ into the devices to give chemiresistive detectors for vapors of thioethers. We also show that incorporating permanaganate into the polymer leads to a chemiresistive detector for VOCs susceptible to oxidation. In Chapter 6, we employ 2-D metal-organic frameworks as chemiresistors for the detection of volatile compounds, exploiting their intrinsic conductivity. These materials are the first of their class to be utilized as chemiresistive detectors because of their uniquely high conductivities.<br>by Sophie Liu.<br>Ph. D.
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25

Arroyo, Mar C. "Inorganic Carbon Chemistry In East Antarctic Coastal Polynyas." W&M ScholarWorks, 2020. https://scholarworks.wm.edu/etd/1593091839.

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Polynyas are large areas of open water or reduced sea ice coverage that persistently form in polar environments and often experience enhanced rates of physical, chemical, and biological processes that impact ocean dynamics on local to global scales. Polynyas that form adjacent to the coast, known as coastal polynyas, play an important role in the global carbon cycle by regulating the exchange of CO2 between the ocean and atmosphere in the high latitudes. Because of their importance to the global carbon cycle, there is a particular interest to better characterize CO2 system processes in Antarctic coastal polynyas. In this study, the inorganic carbon chemistry in three East Antarctic coastal polynyas - the Dalton Polynya, the Mertz Polynya, and the Ninnis Polynya - is investigated using a combination of ship-board water column and underway observations, remote sensing products, and model outputs. The first biogeochemical observations in the Dalton Polynya are presented, and the physical and biological controls on total dissolved inorganic carbon (TCO2) are examined. Despite the evidence of TCO2 depletion due to biological production, the surface waters of the Dalton Polynya were a weak net source of CO2 to the atmosphere during the summer survey. Satellite estimates of sea surface chlorophyll a concentration suggest that the shipboard observations were made prior to the peak of the productive season and are more likely representative of the transition between spring and summer. Compared to coastal polynyas, the rates of net community production and air-sea CO2 exchange in the Dalton polynya were relatively small.
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26

Zain, S. A. M. "Novel inorganic anion exchangers." Thesis, University of Salford, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.234769.

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27

Desmangles, Nathalie. "Chemistry of medium-valent vanadium amide complexes." Thesis, University of Ottawa (Canada), 1998. http://hdl.handle.net/10393/4519.

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The chemistry of low-valent vanadium was extensively investigated especially in the organometallic field. Apart from cyclopentadienyl and alkoxides (or aryloxides) derivatives, its chemistry is poorly developed. Among the supporting ligands for the stabilization of low-valent vanadium, alkylamides need to be studied in more details. By introducing bulky amides such as $\rm R\sb2N\sp-\ (R = \sp{i}Pr,$ Cy, $\rm SiMe\sb3,\ C\sb6H\sb5,$ 3,5-Me$\sb2$Ph and Ad) in chemistry of vanadium(III) and vanadium(IV), we have opened a new field in the coordination of this early transition metal. Synthetic methodology is focused on the preparation of novel tris(amide) vanadium(III) complexes via transmetallation reaction of $\rm VCl\sb3(THF)\sb3$ with $\rm R\sb2NLi,$ using the stoichiometry ratio 1:3 and the same reaction conditions. Reaction of $\rm VCl\sb3(THF)\sb3$ with $\rm\lbrack(CH\sb3)\sb3Si\rbrack NPhLi$ led to the formation of the corresponding tetrahedral $\rm\{\lbrack(CH\sb3)\sb3Si\rbrack NPh\}\sb3V(THF)$ complex. Conversely, the reaction of $\rm CH\sb3C\lbrack(CH\sb2)N(\sp{i}Pr)Li\rbrack\sb3(TIAME)$ with VCl3(THF)$\sb3$ gave the new dinitrogen complex (TIAME)V-N$\sb2$-V(TIAME) whose structure was determined by X-ray analysis. The reaction of VCl$\sb3$(THF)$\sb3$ with (3,5-Me$\sb2$Ph)AdNLi.Et$\sb2$O (Ad = adamantyl) yielded the homoleptic vanadium(III) complex ((3,5-$\rm Me\sb2Ph)AdN\rbrack\sb3V$ which reacts with chalcogens E (E = S, Se) to yield diamagnetic terminal chalcogenide derivatives. The use of low-valent vanadium in the polymerization of olefins is poorly developed apart from acetylacetonato derivatives and chloride derivatives. The complexes of formula $\rm(R\sb2N)\sb2VCl\sb2$ (R = $\rm\sp{i}$Pr, Cy) provide a unique example of oxidative disproportionation. The formation of dicyclahexyl and diisopropyl derivatives is the result of oxidative coupling of two low-valent vanadium entities. The first to be formed is the bis(amido)V$\rm\sp{IV}Cl\sb2$ followed by the unstable "$\rm V\sp{II}Cl\sb2$". The stability of the novel vanadium(IV) bisamido complexes allowed us to investigate their reactivity towards olefin polymerization.
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28

Yau, John. "The chemistry of gold(I) compounds." Thesis, Imperial College London, 1996. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.338901.

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29

Kelland, Malcolm. "Organo-transition metal boron hydride chemistry." Thesis, University of Oxford, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.258164.

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30

Forward, Jennifer Mary. "Aspects of metallocarborane and gold chemistry." Thesis, University of Oxford, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.316885.

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31

Walker, Susan M. "Structure evolution in hydrothermal uranium chemistry." Thesis, University of Oxford, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.249301.

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32

King, Jennifer L. "Organometallic chemistry in supercritical fluid solution." Thesis, University of Nottingham, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.262952.

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33

Thompsett, Andrew Robert. "The coordination chemistry of unusual alkynes." Thesis, University of Warwick, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.302650.

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34

Cathey, Christopher. "Some studies in osmium cluster chemistry." Thesis, University of Cambridge, 1994. https://www.repository.cam.ac.uk/handle/1810/272644.

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35

Botos, Ákos. "Inorganic materials in hollow carbon nanostructures." Thesis, University of Nottingham, 2016. http://eprints.nottingham.ac.uk/31915/.

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The interactions of metal-containing molecules and nanoparticles (NPs) with the interior of hollow graphitic carbon nanostructures (CNs) were investigated and their chemical transformations in the nanoscale channels of CNs appraised. The gas phase insertion of Group VI metal hexacarbonyl complexes (M(CO)6, M=Cr, Mo, W) into CNs was successfully developed and optimised to provide good filling rates as confirmed by transition electron microscopy (TEM). Infrared (IR) and Raman spectroscopy demonstrated that Group VI M(CO)6 complexes with greater polarisability exhibit stronger van der Waals interactions with the interior of single walled carbon nanotubes (SWNTs). The synthesis of metal based NPs inside graphitised carbon nanofibers (GNFs) by the in situ transformation of the encapsulated M(CO)6 precursor molecules was successfully achieved and it was demonstrated that GNFs can act as a source of oxygen in these reactions. The nanotube filling methodology was applied for the multi-step synthesis of new inorganic materials inside CNs by the controlled reactions of M(CO)6, I2 and H2S. This approach yielded unusual van der Waals hybrid materials such as “tube inside a tube” and other hybrid structures of MoS2 and GNFs. In SWNTs, with significantly narrower diameters than GNFs or multi-walled carbon nanotubes (MWNTs), metal complexes form unique 1D arrays of octahedral [M6I14]2- clusters with the nanotube acting as a nanocontainer and a poly-cation balancing the charge of the guest-clusters. The iodides of Mo and W were effectively converted into extremely thin MS2 nanoribbons (NRs) within SWNTs, providing a new more efficient route to the hybrid inorganic nanostructures. In MWNTs, the [Mo6Ii8Ia2Ia a4/2] clusters are packed in a hexagonal pattern to optimise filling of the void, and when reacted with H2S they provide a range of multi-layered MS2NRs with their widths controlled by the internal diameter of the host nanotube.
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36

Hernández, Sánchez Raúl. "Coordination Chemistry and Electronic Structure of Iron Clusters." Thesis, Harvard University, 2015. http://nrs.harvard.edu/urn-3:HUL.InstRepos:17467181.

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Mixed valence compounds have been recognized over the past five decades as a unique class of chemical species. Their distinctive spectral, electrochemical, physical and magnetic properties arise from electron delocalization into the sites with uneven valence. A primary consequence of this electron delocalization phenomenon is the stabilization of high spin multiplicities in certain dinuclear synthetic and polynuclear biological clusters. Therefore, the subject of this dissertation is to extend the current knowledge of the analysis of synthetic mixed valence clusters by systematically altering the coordination chemistry and redox states at well-defined synthetic, polynuclear iron clusters. A central focus of this thesis is to investigate the effect of superexchange, direct exchange, and double exchange electronic coupling in dinuclear [Fe2], trinuclear [Fe3], hexanuclear [Fe6], and octanuclear [Fe8] clusters with the goal of better understanding the principles that govern their complex electronic structures. It is concluded that the resulting electronic structure in these polynuclear systems is highly dependent on the extent of electron delocalization which can be tuned by solvation, anation, or chemical redox changes. This finding is highlighted by the observation that small variations on the solvation coordination sphere and redox level one can transverse spin ground states from S = 0 to S = 11 by addition of 6e– into [Fe6].<br>Chemistry and Chemical Biology
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37

Schneider, William Frederich. "Applications of local-density-functional methods to inorganic chemistry /." The Ohio State University, 1991. http://rave.ohiolink.edu/etdc/view?acc_num=osu1487688973685734.

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38

Wheildon, Andrew R. "Novel nitrogen chemistry." Thesis, University of Nottingham, 1999. http://eprints.nottingham.ac.uk/13326/.

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Chapter One contains a brief overview of zeolites, their structure, uses and synthesis. Chapter Two relates to the attempted synthesis of quinuclidines via a novel 6-endo-trig radical cyclisation. Chapter Three contains a review of the 'Zip reaction' and the attempted synthesis of triazacyclopentadecane derivatives. Chapter Four relates to the synthesis of pyrrolidines via retro-Cope cyclisation methodology. Reviews of the Cope and retro-Cope reactions, nitrone synthesis and nucleophilic addition of carbon nucleophiles to nitrones are included. The synthetic work is split into three sections relating to the electron withdrawing group used to stabilise the carbanion of the nucleophile - ester, sulphone and sulphoxide - and attempts to indicate the utility of the retro-Cope reaction in the diastereoselective synthesis of substituted pyrrolidines.
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Cowie, A. G. "Aspects of transition metal carbidocarbonyl cluster chemistry." Thesis, University of Cambridge, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.356670.

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Trivedi, Madhuri Krashnakant. "The chemistry and application of strontium compounds." Thesis, Brunel University, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.337672.

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Fox, Judith M. "Synthetic and structural aspects of fullerene chemistry." Thesis, University of Oxford, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.361936.

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Metcalfe, John Edwin. "Studies in nickel and manganese coordination chemistry." Thesis, Queen's University Belfast, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.263502.

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Odedra, Rajesh. "Chemistry of platinum and palladium agostic centres." Thesis, University of Salford, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.244934.

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Macpherson, I. "Some metallaborane chemistry of molybdenum and tungsten." Thesis, University of Leeds, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.376799.

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Nestor, Karl. "Some new chemistry of iridaboranes and iridaheteroboranes." Thesis, University of Leeds, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.330000.

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Al-Shamma, F. A. A. A. "Spectroscopic studies of the chemistry of silver." Thesis, Bucks New University, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.376422.

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Champness, Neil Robert. "Studies in ruthenium and osmium coordination chemistry." Thesis, University of Southampton, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.239648.

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Apte, S. C. "The aquatic chemistry of some metalloid elements." Thesis, University of Southampton, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.304812.

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Orchard, Simon David. "Synthesis and coordination chemistry of telluroether ligands." Thesis, University of Southampton, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.326303.

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Prior, Neville D. "Some organometallic chemistry of osmium carbonyl clusters." Thesis, University of Cambridge, 1988. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.257045.

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