subject:(Inorganic Chemistry)

University of Helsinki

1. Sumerin, Victor. Lewis Acid-Lewis Base Mediated Metal-Free Hydrogen Activation and Catalytic Hydrogenation.

Degree: Department of Chemistry, Laboratory of Inorganic Chemistry, 2011, University of Helsinki

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Organocatalysis, the use of organic molecules as catalysts, is attracting increasing attention as one of the most modern and rapidly growing areas of organic chemistry,… (more)

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Organocatalysis, the use of organic molecules as catalysts, is attracting increasing attention as one of the most modern and rapidly growing areas of organic chemistry, with countless research groups in both academia and the pharmaceutical industry around the world working on this subject. The literature review of this thesis mainly focuses on metal-free systems for hydrogen activation and organocatalytic reduction. Since these research topics are relatively new, the literature review also highlights the basic principles of the use of Lewis acid-Lewis base pairs, which do not react irreversibly with each other, as a trap for small molecules. The experimental section progresses from the first observation of the facile heterolytical cleavage of hydrogen gas by amines and B(C6F5)3 to highly active non-metal catalysts for both enantioselective and racemic hydrogenation of unsaturated nitrogen-containing compounds. Moreover, detailed studies of structure-reactivity relationships of these systems by X-ray, neutron diffraction, NMR methods and quantum chemical calculations were performed to gain further insight into the mechanism of hydrogen activation and hydrogenation by boron-nitrogen compounds.

Organokatalyysi, eli pienten orgaanisten molekyylien käyttö katalyytteinä, herättää yhä enemmän kiinnostusta ja on yksi nopeimmin kasvavista modernin orgaanisen kemian tutkimusaloista. Tutkimusta tehdään kansainvälisesti lukuisissa ryhmissä, niin akateemisessa maailmassa kuin lääketeollisuudessa. Tämän väitöskirjan kirjallisuuskatsaus käsittelee metallittomia menetelmiä vedyn aktivoinnissa sekä organokatalyyttistä pelkistystä. Koska nämä tutkimusaiheet ovat suhteellisen uusia, kirjallisuustarkastelu sisältää myös pääperiaatteet reversiibelisti reagoivien Lewis happo- Lewis emäs-parien käytöstä pienten molekyylien loukkuina. Kokeellisessa osassa esitellään kaasumaisen vedyn heterolyyttinen pilkkominen amiineilla ja B(C6F5)3:lla, erittäin aktiivisia metallittomia katalyyttejä sekä enantioselektiivisten ja raseemisten tyydyttymättömien typpiyhdisteiden vedytys. Näiden menetelmien reaktiivisuuden riippuvuutta rakenteista tutkittiin yksityiskohtaisesti röntgendiffraktiolla, neutronidiffraktiolla, NMR-spektroskopialla ja kvanttikemiallisten laskujen avulla. Näin saatiin tarkempi kuva reaktiomekanismeista vedynaktivoinnissa ja pelkistyksissä boori-typpi yhdisteillä.

Subjects/Keywords: inorganic Chemistry; inorganic Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Sumerin, V. (2011). Lewis Acid-Lewis Base Mediated Metal-Free Hydrogen Activation and Catalytic Hydrogenation. (Doctoral Dissertation). University of Helsinki. Retrieved from http://hdl.handle.net/10138/27781

Chicago Manual of Style (16^th Edition):

Sumerin, Victor. “Lewis Acid-Lewis Base Mediated Metal-Free Hydrogen Activation and Catalytic Hydrogenation.” 2011. Doctoral Dissertation, University of Helsinki. Accessed February 23, 2020. http://hdl.handle.net/10138/27781.

MLA Handbook (7^th Edition):

Sumerin, Victor. “Lewis Acid-Lewis Base Mediated Metal-Free Hydrogen Activation and Catalytic Hydrogenation.” 2011. Web. 23 Feb 2020.

Vancouver:

Sumerin V. Lewis Acid-Lewis Base Mediated Metal-Free Hydrogen Activation and Catalytic Hydrogenation. [Internet] [Doctoral dissertation]. University of Helsinki; 2011. [cited 2020 Feb 23]. Available from: http://hdl.handle.net/10138/27781.

Council of Science Editors:

Sumerin V. Lewis Acid-Lewis Base Mediated Metal-Free Hydrogen Activation and Catalytic Hydrogenation. [Doctoral Dissertation]. University of Helsinki; 2011. Available from: http://hdl.handle.net/10138/27781

University of Helsinki

2. Chernichenko, Kostiantyn. Metal-free hydrogenations catalyzed by frustrated ansa-aminoboranes.

Degree: Department of Chemistry, Laboratory of Inorganic Chemistry, 2013, University of Helsinki

URL: http://hdl.handle.net/10138/41098

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Frustrated Lewis pairs (FLPs) are powerful, typically nonmetal, Lewis acid/base combinations that can split dihydrogen (H2) heterolytically, due to their inability to form conventional Lewis… (more)

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Frustrated Lewis pairs (FLPs) are powerful, typically nonmetal, Lewis acid/base combinations that can split dihydrogen (H2) heterolytically, due to their inability to form conventional Lewis adducts (usually as a result of steric repulsion). The H2 thus activated can be transferred to various substrates in a catalytic fashion. The scope of substrates catalytically hydrogenated with FLPs is rapidly expanding, approaching that of transition-metal-catalyzed hydrogenations. The discovery of FLPs is, perhaps, one of the most remarkable recent findings in the field of main group organometallic compounds. The literature review part provides a brief critical overview of heterolytic H2 splitting with FLPs, including the thermodynamic, mechanistic, and catalytic aspects of this process. Particular emphasis is placed on the Lewis acidity of various boranes, since this factor is critical for the ability of FLPs to split H2 and provides a basis for introducing fluoroaryl-free boranes into the FLP area. The experimental section of the thesis is devoted to the development of FLP catalysts, based on an ansa-aminoborane core for hydrogenation of various substrates. Within the study, various parts of the ansa-aminoborane molecule were modified: a amine group, resulting in highly active ansa-aminoboranes for hydrogenation of imines and other nitrogen-containing compounds, also featuring other unique properties; a mutual B/N geometry (changing the nature of the link), resulting in an ansa-catalyst for hydrogenation of unactivated alkynes; and a borane part, revealing that lightweight and inexpensive ansa-aminochloroboranes show reactivity to H2 similar to that of C6F5 boranes, including catalytic abilities. A book chapter covering recent progress in frustrated borane/amine Lewis interaction, involving ansa-systems was included in the thesis.

Molekyylien pelkistäminen vetykaasulla on orgaanisen kemian tärkeimpiä reaktioita. Useimmiten reaktio ei etene itsestään, vaan siihen tarvitaan katalyytti. Vedytyskatalyytit sisältävät tavallisesti kalliita jalometalleja kuten palladiumia, platinaa, rodiumia tai ruteniumia. Vety siirtyy substraatille labiilin metalli-H2 välituotteen kautta. Hiljattain on osoitettu, että tietynlaiset metallittomat yhdisteet, joita kutsutaan turhautuneiksi Lewis-pareiksi, voivat reagoida vedyn kanssa ja jopa toimia katalyytteina monissa pelkistysreaktiossa. Tässä työssä käsitellään yhdisteitä, joiden aktiiviset keskukset, boori ja typpi, on tuotu samassa molekyylissä toistensa lähelle (ansa-aminoboraanit). Nämä ovat tehokkaita vedytyskatalyytteja monille erilaisille substraateille. Työssä syntetisoitiin myös moolimassaltaan kevyitä aminoboraaneja, jotka osoittavat mahdollisuuden käyttää tällaisia yhdisteitä vedyn varastointia varten.

Subjects/Keywords: inorganic chemistry; inorganic chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Chernichenko, K. (2013). Metal-free hydrogenations catalyzed by frustrated ansa-aminoboranes. (Doctoral Dissertation). University of Helsinki. Retrieved from http://hdl.handle.net/10138/41098

Chicago Manual of Style (16^th Edition):

Chernichenko, Kostiantyn. “Metal-free hydrogenations catalyzed by frustrated ansa-aminoboranes.” 2013. Doctoral Dissertation, University of Helsinki. Accessed February 23, 2020. http://hdl.handle.net/10138/41098.

MLA Handbook (7^th Edition):

Chernichenko, Kostiantyn. “Metal-free hydrogenations catalyzed by frustrated ansa-aminoboranes.” 2013. Web. 23 Feb 2020.

Vancouver:

Chernichenko K. Metal-free hydrogenations catalyzed by frustrated ansa-aminoboranes. [Internet] [Doctoral dissertation]. University of Helsinki; 2013. [cited 2020 Feb 23]. Available from: http://hdl.handle.net/10138/41098.

Council of Science Editors:

Chernichenko K. Metal-free hydrogenations catalyzed by frustrated ansa-aminoboranes. [Doctoral Dissertation]. University of Helsinki; 2013. Available from: http://hdl.handle.net/10138/41098

University of Helsinki

3. Tomczak, Yoann. In situ characterization of ALD processes and study of reaction mechanisms for high-k metal oxide formation.

Degree: Department of Chemistry, Laboratory of Inorganic Chemistry, 2014, University of Helsinki

URL: http://hdl.handle.net/10138/45268

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Atomic Layer Deposition (ALD) is a thin film deposition method allowing the growth of highly conformal films with atomic level thickness and composition precision. For… (more)

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Atomic Layer Deposition (ALD) is a thin film deposition method allowing the growth of highly conformal films with atomic level thickness and composition precision. For most of the ALD processes developed, the reaction mechanisms occurring at each step of the deposition remain unclear. Learning more about these reactions would help to control and optimize the existing growth processes and develop new ones more quickly. For that purpose, in situ methods such as quartz crystal microbalance (QCM) and quadrupole mass spectrometer (QMS) are used. These techniques present numerous advantages because they allow monitoring the thin film growth mechanisms directly during the process. Additionally, they do not require separate experiments or large amounts of precursors to test the efficiency of new processes and could be very effective means to monitor industrial processes in real time. This thesis explores the most common in situ analytical methods used to study ALD processes. A review on the ALD metal precursors possessing ligands with nitrogen bonded to the metal center and their reactivity is provided. The results section reports the reaction mechanisms of ALD processes for the deposition of Nb2O5, Ta2O5, Li2SiO3, TiO2 and ZrO2. All the processes studied are using metal precursors with nitrogen bonded ligands and ozone or water for the deposition of high-k and other oxide films.

Atomikerroskasvatus (Atomic Layer Deposition, ALD) on ohutkalvojen kasvatusmenetelmä, jonka avulla pystytään kasvattamaan tarkasti atomikerrosten paksuisia ja erittäin konformaalisia kalvoja. Useimpien ALD-prosessien reaktiomekanismit ovat vielä huonosti tunnettuja. Reaktiomekanismien tutkiminen on tärkeää, sillä se auttaa sekä ymmärtämään paremmin jo tunnettuja prosesseja että kehittämään nopeammin uusia. Tähän tarkoitukseen käytetään in situ -menetelmiä, kuten kvartsikidemikrovaakaa (quartz crystal microbalance, QCM) sekä kvadrupolimassaspektrometria (quadrupole mass spectrometer, QMS). Näillä menetelmillä on lukuisia etuja, sillä niiden avulla ohutkalvojen kasvumekanismeja pystytään tarkastelemaan kasvatusprosessin aikana. Lisäksi niiden käyttämiseen ei tarvita suuria määriä lähtöaineita ja ne voivat olla tehokkaita menetelmiä myös teollisten prosessien reaaliaikaisessa seurannassa. Tässä tutkielmassa perehdytään yleisimpiin ALD-prosessien tutkimisessa käytettäviin in situ -menetelmiin. Tutkielmassa on myös kirjallisuuskatsaus sellaisista ALD-metallilähtöaineista, joissa ligandit ovat sitoutuneet metalliatomiin typpiatomin kautta. Väitöskirjan kokeellisessa osassa on tutkittu Nb2O5:n, Ta2O5:n, Li2SiO3:n, TiO2:n ja ZrO2:n ALD-prosessien reaktiomekanismeja. Kaikissa näissä prosesseissa on käytetty edellä mainitun kaltaisia metalli-typpi-sidoksen sisältäviä metallilähtöaineita sekä otsonia tai vettä.

Subjects/Keywords: inorganic chemistry; inorganic chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Tomczak, Y. (2014). In situ characterization of ALD processes and study of reaction mechanisms for high-k metal oxide formation. (Doctoral Dissertation). University of Helsinki. Retrieved from http://hdl.handle.net/10138/45268

Chicago Manual of Style (16^th Edition):

Tomczak, Yoann. “In situ characterization of ALD processes and study of reaction mechanisms for high-k metal oxide formation.” 2014. Doctoral Dissertation, University of Helsinki. Accessed February 23, 2020. http://hdl.handle.net/10138/45268.

MLA Handbook (7^th Edition):

Tomczak, Yoann. “In situ characterization of ALD processes and study of reaction mechanisms for high-k metal oxide formation.” 2014. Web. 23 Feb 2020.

Vancouver:

Tomczak Y. In situ characterization of ALD processes and study of reaction mechanisms for high-k metal oxide formation. [Internet] [Doctoral dissertation]. University of Helsinki; 2014. [cited 2020 Feb 23]. Available from: http://hdl.handle.net/10138/45268.

Council of Science Editors:

Tomczak Y. In situ characterization of ALD processes and study of reaction mechanisms for high-k metal oxide formation. [Doctoral Dissertation]. University of Helsinki; 2014. Available from: http://hdl.handle.net/10138/45268

McMaster University

4. Elder, Philip J. Experimental and Computational Studies on the Effect of Secondary Bonding Interactions on the Spectroscopic Properties and Reactivity of Organo-chalcogen Compounds.

Degree: PhD, 2011, McMaster University

URL: http://hdl.handle.net/11375/11773

► This thesis presents the results of investigations on the application of modern spectroscopic techniques to the characterisation of secondary bonding interactions (SBIs) in selected… (more)

▼ This thesis presents the results of investigations on the application of modern spectroscopic techniques to the characterisation of secondary bonding interactions (SBIs) in selected organo-chalcogen compounds. Although the research was mostly focused on two families of compounds, ditellurides and chalcogen-substituted azodyes, the observations and conclusions are applicable to a wide variety of compounds. Because the effects of the SBIs are subtle, great care was taken to carefully distinguish contributions from other factors. DFT computational studies showed that the molecular conformation influences the electronic excitations observable in the UV-vis spectrum and the frequency of resonance in ¹²⁵Te NMR of organoditellurides. In the absence of protection to shield the chalcogen from intermolecular interactions, the ¹²⁵Te NMR chemical shift is dependent on the concentration of ditellurides; intramolecular SBIs attenuate the concentration dependency and steric protection cancels it entirely. The nature of the solvent impacts the results of both spectroscopic techniques through several mechanisms, including the solvatochromic effect, conformational changes due to the polarity of the medium and solvation. Solution ¹²⁵Te NMR spectroscopy is sensitive to all those contributions but, for the same reason, it cannot be applied in an unambiguous way to identify the presence of SBIs. Conversely, the use of intramolecular SBIs to modify the spectroscopic properties of a conjugated chromophore was investigated. Push-pull azobenzenes were derivatised with functional groups containing divalent chalcogen atoms through metathesis with a mercurated derivative of the azodye. The regiochemistry of formation of the intermediate was shown to be under kinetic control. In the chalcogen-substituted molecules, the efficiency of electron delocalisation through the SBIs was assessed by calculations of the nucleus independent chemical shift (NICS). The linear (UV-vis absorption) and nonlinear (second harmonic-generation) optical responses of the modified chromophore were investigated and interpreted in the context of the SBIs. Substitution with the chalcogen groups, and the consequent perturbation of the π-system, cause a blue shift in the first absorption maxima but little change was observed in the hyperpolarisability of the chromophore ortho-functionalised with the phenylselenenyl group. The sensitivity of the electronic spectrum to the SBI was applied to monitor the process of halide exchange in the halo-chalcogenyl derivatives of the push-pull azobenzene. Very strong SBIs can result in interatomic distances so short that they are difficult to distinguish from hypervalent covalent bonds. This is the situation observed in the structure of the first 2,5,8,11,1,4,7,10,3,6,9,12-tetraoxatetratelluratetrazacyclododecane. DFT calculations showed that this unusual macrocycle is stable with respect to dissociation into isotellurazole oxide and VT NOESY experiments indicate it remains intact in… Advisors/Committee Members: Vargas-Baca, Ignacio, Chemistry.

Subjects/Keywords: Inorganic Chemistry; Inorganic Chemistry

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APA (6^th Edition):

Elder, P. J. (2011). Experimental and Computational Studies on the Effect of Secondary Bonding Interactions on the Spectroscopic Properties and Reactivity of Organo-chalcogen Compounds. (Doctoral Dissertation). McMaster University. Retrieved from http://hdl.handle.net/11375/11773

Chicago Manual of Style (16^th Edition):

Elder, Philip J. “Experimental and Computational Studies on the Effect of Secondary Bonding Interactions on the Spectroscopic Properties and Reactivity of Organo-chalcogen Compounds.” 2011. Doctoral Dissertation, McMaster University. Accessed February 23, 2020. http://hdl.handle.net/11375/11773.

MLA Handbook (7^th Edition):

Elder, Philip J. “Experimental and Computational Studies on the Effect of Secondary Bonding Interactions on the Spectroscopic Properties and Reactivity of Organo-chalcogen Compounds.” 2011. Web. 23 Feb 2020.

Vancouver:

Elder PJ. Experimental and Computational Studies on the Effect of Secondary Bonding Interactions on the Spectroscopic Properties and Reactivity of Organo-chalcogen Compounds. [Internet] [Doctoral dissertation]. McMaster University; 2011. [cited 2020 Feb 23]. Available from: http://hdl.handle.net/11375/11773.

Council of Science Editors:

Elder PJ. Experimental and Computational Studies on the Effect of Secondary Bonding Interactions on the Spectroscopic Properties and Reactivity of Organo-chalcogen Compounds. [Doctoral Dissertation]. McMaster University; 2011. Available from: http://hdl.handle.net/11375/11773

Iowa State University

5. Dairo, Taiwo Olawale. Iridium porphyrin synthesis, reactivity and catalysis, and the nanogold-catalyzed synthesis of lactams.

Degree: 2016, Iowa State University

URL: https://lib.dr.iastate.edu/etd/15146

► The work presented in this report focuses on the synthesis and characterization of new iridium(III) porphyrin complexes, the iridium porphyrin-catalyzed insertion of diazo esters into… (more)

▼ The work presented in this report focuses on the synthesis and characterization of new iridium(III) porphyrin complexes, the iridium porphyrin-catalyzed insertion of diazo esters into the S-H bond of thiols (S-H insertion), and the efficient nanogold-catalyzed oxidation of amines into lactams, in the presence of atmospheric oxygen. Preliminary results of the nanogold-catalyzed synthesis of N,N'-disubstituted ureas from the room temperature reaction between primary amines, carbon monoxide and oxygen, are presented as well. Upon treatment of (carbonyl)chloro(meso-tetra-p-tolylporphyrinato)iridium(III), (TTP)Ir(CO)Cl, with excess primary amines (amine = RNH2 = benzylamine, n-butylamine, isopropylamine, and tert-butylamine), at 23 ºC, in the presence of Na2CO3, trans-amine-coordinated iridium carbamoyl complexes, (TTP)Ir(NH2R)[C(O)NHR], were isolated in yields up to 94%. The lability of the amine ligands was established by variable-temperature NMR studies, ligand replacement reactions, and equilibrium binding studies. Consequently, hexacoordinate complexes of the type (TTP)Ir(L)[C(O)NHR] were synthesized, where L included quinuclidine, 1-methylimidazole, triethylphosphite, and dimethylphosphine. A series of ligand binding studies showed that both electronic and steric factors influenced ligand binding to the metal center. Furthermore, the nature of the trans ligand determined the reactivity of the carbamoyl ligand with the electrophile HBF4. On the other hand, the carbamoyl ligand reacted with CH3I in a similar fashion, whether the trans ligand contained a nitrogen or phosphorus donor. This work also reports that the pentacoordinated Ir(TTP)CH3 efficiently catalyzed the insertion of the carbene moieties from methyl diazoacetate (MDA), ethyl diazoacetate (EDA), methyl phenyldiazoacetate (MPDA) and methyl (p-tolyl)diazoacetate (MTDA) into the S-H bond of different aromatic and aliphatic thiols. Product yields ranged from 70 – 97%. UV-visible titration showed that electron-rich thiols bind more strongly to iridium than their electron-poor counterparts. Substrate competition and trapping experiments also suggested that the insertion reactions proceed via an ylide intermediate. Furthermore, kinetic experiments showed that the observed reaction rates were a consequence of the competitive binding of thiol to the metal center of the catalyst and the nucleophilic attack of the thiol on the metal carbene intermediate. The oxidation of cyclic amines into lactams was efficiently catalyzed by CeO2-supported gold nanoparticles (Au/CeO2) in the presence of 1 atmosphere of O2. The complete conversion of pyrrolidine was achieved in 6.5 hours at 160 °C, affording a 97% yield of the lactam product 2-pyrrolidone (γ-butyrolactam), while 2-piperidone (δ-valerolactam) was synthesized from piperidine (83% yield) in of 2.5 hours. Caprolactam, the precursor to nylon-6, was obtained from hexamethyleneimine in 37% yield in 3 hours. The intermediacy of 5-(pyrrolidin-1-yl)-3,4-dihydro-2H-pyrrole (amidine-5) and 4-amino-1-(pyrrolidin-1-yl)butan-1-one)…

Subjects/Keywords: Inorganic Chemistry; Inorganic Chemistry

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APA (6^th Edition):

Dairo, T. O. (2016). Iridium porphyrin synthesis, reactivity and catalysis, and the nanogold-catalyzed synthesis of lactams. (Thesis). Iowa State University. Retrieved from https://lib.dr.iastate.edu/etd/15146

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Dairo, Taiwo Olawale. “Iridium porphyrin synthesis, reactivity and catalysis, and the nanogold-catalyzed synthesis of lactams.” 2016. Thesis, Iowa State University. Accessed February 23, 2020. https://lib.dr.iastate.edu/etd/15146.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Dairo, Taiwo Olawale. “Iridium porphyrin synthesis, reactivity and catalysis, and the nanogold-catalyzed synthesis of lactams.” 2016. Web. 23 Feb 2020.

Vancouver:

Dairo TO. Iridium porphyrin synthesis, reactivity and catalysis, and the nanogold-catalyzed synthesis of lactams. [Internet] [Thesis]. Iowa State University; 2016. [cited 2020 Feb 23]. Available from: https://lib.dr.iastate.edu/etd/15146.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Dairo TO. Iridium porphyrin synthesis, reactivity and catalysis, and the nanogold-catalyzed synthesis of lactams. [Thesis]. Iowa State University; 2016. Available from: https://lib.dr.iastate.edu/etd/15146

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

6. Pindwal, Aradhana. Lanthanide alkyl and silyl compounds: synthesis, reactivity and catalysts for green chemistry.

Degree: 2016, Iowa State University

URL: https://lib.dr.iastate.edu/etd/15091

► The last few decades have witnessed enormous research in the field of organometallic lanthanide chemistry. Our research group has developed a few rare earth alkyl… (more)

▼ The last few decades have witnessed enormous research in the field of organometallic lanthanide chemistry. Our research group has developed a few rare earth alkyl compounds containing tris(dimethylsilyl)methyl ligand and explored their reactivity. This thesis focusses on extending the study of lanthanide alkyl and silyl compounds to develop strategies for their synthesis and explore their reactivity and role as catalysts in processes such as hydrosilylation and cross-dehydrocoupling. Two novel ligands, alkyl, –C(SiHMe2)3 and silyl, –Si(SiHMe2)3 have been used to synthesize homoleptic organometallic lanthanide complexes. The silyl anion, KSi(SiHMe2)3, is prepared from the reaction of KOtBu and Si(SiHMe2)4. A single crystal X-ray diffraction study shows that KSi(SiHMe2)3 crystallizes as a chain of alternating K cations and Si(SiHMe2)3 anions with K coordinated to the central Si atoms and the three Si-H moieties oriented toward the next K atom. A series of lanthanum, cerium, praseodymium, neodymium, and samarium alkyl compounds and ytterbium and yttrium silyl compounds are synthesized and their characterization, reactivity and role as catalysts are described. These compounds are synthesized by salt metathesis reaction between the metal halide and an equiv. amount of KC(SiHMe2)3 and KSi(SiHMe2)3 ligands. The lanthanide tris(alkyl) compounds are solvent free compounds while lanthanide bis(silyl) compounds are THF coordinated and unstable at room temperature. All these compounds are highly air- and moisture-sensitive. Interestingly, spectroscopic characterization and X-ray analysis reveal that all the lanthanide alkyl compounds contain classical and non-classical β-SiH interactions with the metal center and undergo β-SiH abstraction by Lewis acids, such as B(C6F5)3 while the lanthanide silyl compounds lack such non-classical interactions with the metal center. The reactions of Ln{C(SiHMe2)3}3 (Ln = La, Ce, Pr, Nd) with one and two equiv. of B(C6F5)3 gives Ln{C(SiHMe2)3}2HB(C6F5)3, and LnC(SiHMe2)3{HB(C6F5)3}2, respectively and an equiv. amount of 1,3-disilacyclobutane dimer, {Me2Si-C(SiHMe2)2}2 as the by-product. The monocations, Ln{C(SiHMe2)3}2HB(C6F5)3 are used as catalysts for hydrosilylation of α,β- unsaturated esters to selectively yield α-silyl esters. α-Silyl esters are isolated in high yields from a range of α,β-unsaturated esters and hydrosilanes. The divalent bis(alkyl) lanthanide compounds, Ln{C(SiHMe2)3}2THF2 (Ln = Yb, Sm) are synthesized by salt metathesis of lanthanide halide and two equiv. of KC(SiHMe2)3 in THF. Reactions with one or two equiv. of B(C6F5)3 generate LnC(SiHMe2)3HB(C6F5)3 and an equiv. amount of 1,3-disilacyclobutane dimer, {Me2Si-C(SiHMe2)2}2. Ln{C(SiHMe2)3}2THF2 undergoes reaction with 1,3-di-tert-butylimidazol-2-ylidene (ImtBu) to yield Ln{C(SiHMe2)3}2ImtBu in non-polar solvent. A single crystal X-ray diffraction and spectroscopic study of Ln{C(SiHMe2)3}2THF2 and Ln{C(SiHMe2)3}2ImtBu reveal the presence of classical and non-classical interactions with the metal center. Ln{C(SiHMe2)3}2ImtBu…

Subjects/Keywords: Inorganic Chemistry; Inorganic Chemistry

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APA (6^th Edition):

Pindwal, A. (2016). Lanthanide alkyl and silyl compounds: synthesis, reactivity and catalysts for green chemistry. (Thesis). Iowa State University. Retrieved from https://lib.dr.iastate.edu/etd/15091

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Pindwal, Aradhana. “Lanthanide alkyl and silyl compounds: synthesis, reactivity and catalysts for green chemistry.” 2016. Thesis, Iowa State University. Accessed February 23, 2020. https://lib.dr.iastate.edu/etd/15091.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Pindwal, Aradhana. “Lanthanide alkyl and silyl compounds: synthesis, reactivity and catalysts for green chemistry.” 2016. Web. 23 Feb 2020.

Vancouver:

Pindwal A. Lanthanide alkyl and silyl compounds: synthesis, reactivity and catalysts for green chemistry. [Internet] [Thesis]. Iowa State University; 2016. [cited 2020 Feb 23]. Available from: https://lib.dr.iastate.edu/etd/15091.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Pindwal A. Lanthanide alkyl and silyl compounds: synthesis, reactivity and catalysts for green chemistry. [Thesis]. Iowa State University; 2016. Available from: https://lib.dr.iastate.edu/etd/15091

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

7. Cooper, Benjamin. EXPLORING THE REACTIVITY OF INDIUM(I) TRIFLATE AND RELATED LOW OXIDATION STATE INDIUM SALTS.

Degree: PhD, Chemistry and Biochemistry, 2011, National Library of Canada

URL: http://scholar.uwindsor.ca/etd/388

► This dissertation's primary focus is on expanding the chemistry of the unusually soluble inorganic indium(I) salt, indium trifluoromethanesulfonate (Indium triflate, InOTf). The utility of InOTf… (more)

Subjects/Keywords: Inorganic Chemistry.

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APA (6^th Edition):

Cooper, B. (2011). EXPLORING THE REACTIVITY OF INDIUM(I) TRIFLATE AND RELATED LOW OXIDATION STATE INDIUM SALTS. (Doctoral Dissertation). National Library of Canada. Retrieved from http://scholar.uwindsor.ca/etd/388

Chicago Manual of Style (16^th Edition):

Cooper, Benjamin. “EXPLORING THE REACTIVITY OF INDIUM(I) TRIFLATE AND RELATED LOW OXIDATION STATE INDIUM SALTS.” 2011. Doctoral Dissertation, National Library of Canada. Accessed February 23, 2020. http://scholar.uwindsor.ca/etd/388.

MLA Handbook (7^th Edition):

Cooper, Benjamin. “EXPLORING THE REACTIVITY OF INDIUM(I) TRIFLATE AND RELATED LOW OXIDATION STATE INDIUM SALTS.” 2011. Web. 23 Feb 2020.

Vancouver:

Cooper B. EXPLORING THE REACTIVITY OF INDIUM(I) TRIFLATE AND RELATED LOW OXIDATION STATE INDIUM SALTS. [Internet] [Doctoral dissertation]. National Library of Canada; 2011. [cited 2020 Feb 23]. Available from: http://scholar.uwindsor.ca/etd/388.

Council of Science Editors:

Cooper B. EXPLORING THE REACTIVITY OF INDIUM(I) TRIFLATE AND RELATED LOW OXIDATION STATE INDIUM SALTS. [Doctoral Dissertation]. National Library of Canada; 2011. Available from: http://scholar.uwindsor.ca/etd/388

8. Hamaed, Hiyam. Solid-State NMR Spectroscopy of Unreceptive Nuclei in Inorganic and Organic Systems.

Degree: PhD, Chemistry and Biochemistry, 2010, National Library of Canada

URL: http://scholar.uwindsor.ca/etd/391

► Nuclei are termed unreceptive if they are not amenable to solid-state NMR (SSNMR) experimentation at standard magnetic field strengths due to (i) low natural abundances… (more)

▼ Nuclei are termed unreceptive if they are not amenable to solid-state NMR (SSNMR) experimentation at standard magnetic field strengths due to (i) low natural abundances or dilution; (ii) low gyromagnetic ratios; (iii) inefficient longitudinal relaxation; (iv) large quadrupole moments; or (v) combinations of these factors. This thesis focuses on applying a variety of SSNMR methods to study unreceptive nuclei in a variety of systems. The first portion of this thesis focuses upon ultra-wideline (UW) SSNMR of three main group nuclei: 209Bi, 137Ba and 115In. 209Bi and 137Ba SSNMR were applied to a series of systems with important structural motifs, while 115In SSNMR was applied to systems with In in the +1 oxidation state. Extremely broad SSNMR spectra were acquired at field strengths of 9.4 and 21.1 T. In all cases, the electric field gradient (EFG) and the chemical shift (CS) tensor parameters obtained from these spectra are used to probe the metal coordination environments. These data are complemented by first principles calculations of the NMR tensors using molecular orbital (MO) and plane wave density functional theory (DFT) methods. The second portion of this thesis examines applications of SSNMR of unreceptive nuclei to some practical problems. First, 109Ag and 15N SSNMR experiments were performed to study silver supramolecular frameworks, and structural changes which occur upon their reactions with primary amines. 1H-109Ag cross polarization/magic-angle spinning (CP/MAS) NMR spectra were used to differentiate Ag sites, and 1H-15N CP/MAS NMR spectra provided measurements of 1J(109Ag, 15N) coupling constants, which are used to probe bonding Ag-N bonding. First principles calculations of silver and nitrogen CS tensors and 1J(109Ag, 15N) constants aided in formulating the structural models for the new materials. Second, 35Cl SSNMR spectra, single-crystal and powder X-ray diffraction data, and ab initio calculations were utilized to study HCl pharmaceuticals and some of their polymorphs. The sensitivity of the 35Cl EFG tensor parameters to subtle changes in the chlorine environments is reflected in the powder patterns, which can be used for structural interpretation, identifying and distinguishing polymorphs, and rapidly providing a spectral fingerprint of each pure pharmaceutical and its polymorphs. Advisors/Committee Members: Schurko, Robert (Chemistry and Biochemistry).

Subjects/Keywords: Chemistry; Inorganic.

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APA (6^th Edition):

Hamaed, H. (2010). Solid-State NMR Spectroscopy of Unreceptive Nuclei in Inorganic and Organic Systems. (Doctoral Dissertation). National Library of Canada. Retrieved from http://scholar.uwindsor.ca/etd/391

Chicago Manual of Style (16^th Edition):

Hamaed, Hiyam. “Solid-State NMR Spectroscopy of Unreceptive Nuclei in Inorganic and Organic Systems.” 2010. Doctoral Dissertation, National Library of Canada. Accessed February 23, 2020. http://scholar.uwindsor.ca/etd/391.

MLA Handbook (7^th Edition):

Hamaed, Hiyam. “Solid-State NMR Spectroscopy of Unreceptive Nuclei in Inorganic and Organic Systems.” 2010. Web. 23 Feb 2020.

Vancouver:

Hamaed H. Solid-State NMR Spectroscopy of Unreceptive Nuclei in Inorganic and Organic Systems. [Internet] [Doctoral dissertation]. National Library of Canada; 2010. [cited 2020 Feb 23]. Available from: http://scholar.uwindsor.ca/etd/391.

Council of Science Editors:

Hamaed H. Solid-State NMR Spectroscopy of Unreceptive Nuclei in Inorganic and Organic Systems. [Doctoral Dissertation]. National Library of Canada; 2010. Available from: http://scholar.uwindsor.ca/etd/391

9. Irfanoglu, Burcin. Synthesis and characterization of porous metal organic framework materials.

Degree: 2012, California State University, Long Beach

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=1511354

► Porous materials have been known since the 18^th century in natural forms of inorganic structures known as zeolites and organic structures known as carbon.… (more)

Subjects/Keywords: Chemistry; Inorganic

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APA (6^th Edition):

Irfanoglu, B. (2012). Synthesis and characterization of porous metal organic framework materials. (Thesis). California State University, Long Beach. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=1511354

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Irfanoglu, Burcin. “Synthesis and characterization of porous metal organic framework materials.” 2012. Thesis, California State University, Long Beach. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=1511354.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Irfanoglu, Burcin. “Synthesis and characterization of porous metal organic framework materials.” 2012. Web. 23 Feb 2020.

Vancouver:

Irfanoglu B. Synthesis and characterization of porous metal organic framework materials. [Internet] [Thesis]. California State University, Long Beach; 2012. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=1511354.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Irfanoglu B. Synthesis and characterization of porous metal organic framework materials. [Thesis]. California State University, Long Beach; 2012. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=1511354

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Montana

10. Hughes, Mark Anthony. The structure function relationship of silica polyamine composites.

Degree: 2008, University of Montana

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=3278312

► The goals of this thesis were to improve the performance of silica polyamine composites by manipulating the surface structure and to understand the relationship… (more)

▼ The goals of this thesis were to improve the performance of silica polyamine composites by manipulating the surface structure and to understand the relationship between, polymer structure and ligand modification of the grafted polyamine. Improvements in silica polyamine composite performance resulted from modifying silica gel with methyltrichlorosilane (MTCS) substituted for a molar fraction of reagent chloropropyltrichlorosilane (CPTCS), which has been traditionally employed. MTCS does not possess a terminal chloride group thus preventing the subsequent attachment of a polyamine to this moiety. MTCS has a smaller molecular volume than CPTCS and as a consequence greater coverage of the silica gel surface by silanes was determined by elemental analysis and NMR. An increase in the fraction of amines not attached to the surface (free amines) allowed improved mass transfer kinetics and in some cases improvements in metal ion sorption capacities of the polymer modified materials. Further, MTCS is cheaper than CPTCS thus allowing a more economically sound synthesis. As a result of an increase in free amines, silica gel polyamine composites were modified with sodium chloroacetate and other metal selective ligands in higher yield, resulting in a material with substantially improved copper ion capacities. Silica polyamine composites have also been modified with a novel series of amino acid chelating ligands for the purpose of selective extraction of heavy metals from aqueous media. The presence of the functional groups was confirmed by ¹³C NMR and elemental analysis. The adsorption properties of modified composites have been determined for divalent and trivalent metal ions. Cycle testing was performed to measure longevity. Selective extraction and recovery of a single metal ion from media containing multiple metal ions has been demonstrated. The structure of the polyamine used has been shown to have a significant impact on the specific selectivity of modified silica polyamine composites even when modified with the same ligand. Potential areas of application have been tested and appear promising. These include an acid mine drainage polluted stream near Helena, MT, as well as synthetic high pressure leach laterite solutions.

Subjects/Keywords: Chemistry; Inorganic

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APA (6^th Edition):

Hughes, M. A. (2008). The structure function relationship of silica polyamine composites. (Thesis). University of Montana. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=3278312

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Hughes, Mark Anthony. “The structure function relationship of silica polyamine composites.” 2008. Thesis, University of Montana. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=3278312.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Hughes, Mark Anthony. “The structure function relationship of silica polyamine composites.” 2008. Web. 23 Feb 2020.

Vancouver:

Hughes MA. The structure function relationship of silica polyamine composites. [Internet] [Thesis]. University of Montana; 2008. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3278312.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Hughes MA. The structure function relationship of silica polyamine composites. [Thesis]. University of Montana; 2008. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3278312

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Colorado State University

11. Newell, Brian S. Synthesis and characterization of uranium(IV) compounds| From mononuclear complexes to multinuclear assemblies.

Degree: 2012, Colorado State University

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=3489959

► This dissertation describes the synthesis of multinuclear compounds that possess magnetically-coupled actinide, namely uranium-238, clusters. These assemblies are supported by both acetylide-type ligands as… (more)

Subjects/Keywords: Chemistry; Inorganic

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APA (6^th Edition):

Newell, B. S. (2012). Synthesis and characterization of uranium(IV) compounds| From mononuclear complexes to multinuclear assemblies. (Thesis). Colorado State University. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=3489959

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Newell, Brian S. “Synthesis and characterization of uranium(IV) compounds| From mononuclear complexes to multinuclear assemblies.” 2012. Thesis, Colorado State University. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=3489959.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Newell, Brian S. “Synthesis and characterization of uranium(IV) compounds| From mononuclear complexes to multinuclear assemblies.” 2012. Web. 23 Feb 2020.

Vancouver:

Newell BS. Synthesis and characterization of uranium(IV) compounds| From mononuclear complexes to multinuclear assemblies. [Internet] [Thesis]. Colorado State University; 2012. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3489959.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Newell BS. Synthesis and characterization of uranium(IV) compounds| From mononuclear complexes to multinuclear assemblies. [Thesis]. Colorado State University; 2012. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3489959

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of California, Irvine

12. Zarkesh, Ryan A. Synthesis, Reactivity, and Multi-Electron Redox Behavior of a Bis(phenoxy)amide Ligand Coordinated to a Tantalum Metal Center.

Degree: 2012, University of California, Irvine

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=3494780

► This dissertation describes the synthesis and reactivity of tantalum metal complexes containing a tridentate redox-active ligand. Fundamental studies have focused on utilizing the redox-active… (more)

Subjects/Keywords: Chemistry; Inorganic

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APA (6^th Edition):

Zarkesh, R. A. (2012). Synthesis, Reactivity, and Multi-Electron Redox Behavior of a Bis(phenoxy)amide Ligand Coordinated to a Tantalum Metal Center. (Thesis). University of California, Irvine. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=3494780

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Zarkesh, Ryan A. “Synthesis, Reactivity, and Multi-Electron Redox Behavior of a Bis(phenoxy)amide Ligand Coordinated to a Tantalum Metal Center.” 2012. Thesis, University of California, Irvine. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=3494780.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Zarkesh, Ryan A. “Synthesis, Reactivity, and Multi-Electron Redox Behavior of a Bis(phenoxy)amide Ligand Coordinated to a Tantalum Metal Center.” 2012. Web. 23 Feb 2020.

Vancouver:

Zarkesh RA. Synthesis, Reactivity, and Multi-Electron Redox Behavior of a Bis(phenoxy)amide Ligand Coordinated to a Tantalum Metal Center. [Internet] [Thesis]. University of California, Irvine; 2012. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3494780.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Zarkesh RA. Synthesis, Reactivity, and Multi-Electron Redox Behavior of a Bis(phenoxy)amide Ligand Coordinated to a Tantalum Metal Center. [Thesis]. University of California, Irvine; 2012. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3494780

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

13. Kurzman, Joshua A. Solid state chemistry of platinum group and noble metal oxides| Implications for heterogeneous catalysis.

Degree: 2012, University of California, Santa Barbara

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=3495690

► The substitution of precious metal ions in oxide hosts represents an attractive alternative to conventional metal-particle-on-oxide catalysts, potentially providing improvements in efficacy and lifetime… (more)

▼ The substitution of precious metal ions in oxide hosts represents an attractive alternative to conventional metal-particle-on-oxide catalysts, potentially providing improvements in efficacy and lifetime while simultaneously reducing the loading of these scarce and expensive elements. This dissertation addresses a range of topics within a theme of understanding the solid state chemistry of platinum group and noble metal ions, with implications for their role in heterogeneous catalysis. To inform an understanding of the crystal chemistry of precious metal-substituted oxides, we begin by examining stoichiometric complex oxide compounds of isoelectronic Au³⁺ and Pd²⁺. La₄LiAuO₈ and La₂BaPdO₅ display exceptional resistance towards thermal dissociation and chemical reduction, serving as model compounds for understanding the crystal chemical conditions that stabilize these oxophobic elements in oxide environments. This understanding is further borne out in a neutron powder diffraction study of La₄LiAuO₈ – the first such study of a stoichiometric (rather than lightly substituted) oxide compound with gold. Recent interest in platinum group metal- (PGM) substitution has been stimulated by findings that certain substituted complex oxides can reversibly extrude and reincorporate the PGM in response to redox changes in the atmosphere to which they are exposed. Of the PGM-substituted complex oxides studied, almost all have been perovskites. Here we present an investigation of Pd²⁺/Pd⁰ redox cycling in a non-perovskite host, hexagonal YMnO₃-type YMn0:5Fe0:5O3. YMn_0.5Fe_0.5-_xPdxO3-δ is only modestly tolerant to removal and redistribution of Pd²⁺; after only a few cycle cycles PdO is formed, rather than Pd2+ being reintegrated into the host. The final study presented here is a computational investigation of electronic structural features in compounds spanning the range of formal oxidation states adopted by gold in extended solids. Guided by the well-established importance of the position at which the transition element d band is centered (relative to the Fermi energy), we find an absence of any correlation between the charge on or oxidation state of Au and the position of the Au 5d-band center. Instead of correlating with the Au charge or oxidation state, the location of the d-band center shows a strong dependence on the degree of its filling.

Subjects/Keywords: Chemistry; Inorganic

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Kurzman, J. A. (2012). Solid state chemistry of platinum group and noble metal oxides| Implications for heterogeneous catalysis. (Thesis). University of California, Santa Barbara. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=3495690

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Kurzman, Joshua A. “Solid state chemistry of platinum group and noble metal oxides| Implications for heterogeneous catalysis.” 2012. Thesis, University of California, Santa Barbara. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=3495690.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Kurzman, Joshua A. “Solid state chemistry of platinum group and noble metal oxides| Implications for heterogeneous catalysis.” 2012. Web. 23 Feb 2020.

Vancouver:

Kurzman JA. Solid state chemistry of platinum group and noble metal oxides| Implications for heterogeneous catalysis. [Internet] [Thesis]. University of California, Santa Barbara; 2012. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3495690.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Kurzman JA. Solid state chemistry of platinum group and noble metal oxides| Implications for heterogeneous catalysis. [Thesis]. University of California, Santa Barbara; 2012. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3495690

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

14. Holmes, Lesley. Study of dynamic processes in unique oxide-ion conduction materials via solid state NMR spectroscopy.

Degree: 2009, State University of New York at Stony Brook

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=3358204

► Detailed examination of the conduction processes in solid oxides identified as potentially beneficial materials for use as electrolytes in solid oxide fuel cells (SOFC's),… (more)

▼ Detailed examination of the conduction processes in solid oxides identified as potentially beneficial materials for use as electrolytes in solid oxide fuel cells (SOFC's), is of tremendous interest. The current study focuses on materials that are of potential interest in forming the electrolyte layer of a SOFC, or as gas sensors or separation membranes. Currently, the most common electrolyte material used in SOFC applications is yttria stabilized zirconia (YSZ). To achieve reasonable levels of conduction through this material, high operating temperatures ≥ 800°C are required. However, devices containing materials which demonstrate reasonable conduction at slightly lower temperatures (≈ 600°C) could potentially be constructed from a wider range of materials i.e. stainless steel. Given the unique and sensitive ability NMR has to examine the subtle dynamic aspects of a system on a localized level, we have undertaken to use this technique to answer some difficult questions regarding several complex ionically conducting solid oxide materials. First, a uniquely constructed, column-containing system of the formula Bi₂₆Mo₁₀O₆₉ was studied because it is compositionally related to materials which have been found to be highly conducting, but has a very unusual structure. This material demonstrated unexpected levels of ionic motion at a tremendously wide range of temperatures. Next, the oxide conduction aspects of the parent as well as lanthanum and gallium doped forms of barium indium oxide (Ba₂In₂O₅) were examined in depth. While NMR spectra have previously been acquired of the end member of this material, a re-examination at higher field strengths revealed new structural information. Lanthanum and gallium doped analogs were examined by ¹⁷O and ⁷¹Ga NMR for the first time. Finally, proton conduction in hydrated analogs of barium indium oxide (Ba₂In₂O₅·H₂O) was examined by variable temperature NMR. Proton conducting hydrates of oxide materials are very useful as electrolytes in intermediate temperature solid oxide fuel cells (ITSOFC). Proton spectra have previously been acquired for this system at room temperature, however, no interpretation as to the structural or dynamic implications of these spectra have yet been undertaken until the current study.

Subjects/Keywords: Chemistry; Inorganic

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APA (6^th Edition):

Holmes, L. (2009). Study of dynamic processes in unique oxide-ion conduction materials via solid state NMR spectroscopy. (Thesis). State University of New York at Stony Brook. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=3358204

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Holmes, Lesley. “Study of dynamic processes in unique oxide-ion conduction materials via solid state NMR spectroscopy.” 2009. Thesis, State University of New York at Stony Brook. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=3358204.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Holmes, Lesley. “Study of dynamic processes in unique oxide-ion conduction materials via solid state NMR spectroscopy.” 2009. Web. 23 Feb 2020.

Vancouver:

Holmes L. Study of dynamic processes in unique oxide-ion conduction materials via solid state NMR spectroscopy. [Internet] [Thesis]. State University of New York at Stony Brook; 2009. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3358204.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Holmes L. Study of dynamic processes in unique oxide-ion conduction materials via solid state NMR spectroscopy. [Thesis]. State University of New York at Stony Brook; 2009. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3358204

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

15. Wikstrom, Jeffrey P. Biomimetic dipicolylamine nickel complexes| Structure and reactivity.

Degree: 2009, Tufts University

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=3379046

► This document comprises the results of over seven years of research in the area of the urease enzyme and its structural modeling. The research… (more)

▼ This document comprises the results of over seven years of research in the area of the urease enzyme and its structural modeling. The research ranges from direct kinetic studies of the urease enzyme, to a series of synthetic model complexes. These featured nickel complexes derive from the 2,2'-dipicolylamine (RDPA) tridentate ligand moiety, with a variety of coordination geometries, nuclearity, and reactivity demonstrated. In Chapter 2, several nickel systems are described, beginning with kinetic studies of the urease enzyme itself, demonstrating that the cyanate anion is not an inhibitor of the enzyme. Spectral studies of multiple nickel complexes are then described, all based on the RDPA ligand moiety, demonstrating urea binding to the 1:1 nickel:ligand complex formed from nickel(II) and tert-butyl-dipicolylamine (tBuDPA) and no observed binding in the 1:2 nickel:ligand complex formed from benzyl-dipicolylamine (BzDPA). The differences in reactivity between these two species are further explored with regards to radical aliphatic hydroxylation. Chapter 2 closes with two stopped-flow studies of nickel species related to the DPA species discussed elsewhere: urea binding to a nickel complex containing a dinucleating ligand with DPA moieties (in collaboration with Prof. Franc Meyer), and oxygen dependence on the reactivity of a trinuclear nickel complex towards an ARD-analog (in collaboration with Prof. Lisa Berreau). Chapter 3 describes the synthesis and characterization of an unusual 4Ni-4OH cubanetype tetrameric species supported by a dipicolylamine ligand DPA lacking a substitutent on its central amine (HDPA). The cubane is characterized crystallographically and magnetically; it demonstrates antiferromagnetic exchange across its bridging hydroxide anions. A brief review of the magnetochemistry of 4Ni-4OR cubane-type clusters is included. In Chapter 4, the effects of a sterically bulky tert-butyl group on the coordination chemistry described in Chapter 3 are presented. Unlike HDPA, tBuDPA prevents formation of a 4Ni-4OH cubane, instead limiting the polynuclearity of the resulting complex to a dimer; the resulting 2Ni-2OH species and its 2Ni-2OMe analog are described. The tetrameric carbonate-bridged species resulting from carbon dioxide fixation by the 2Ni-2OH species is also described. The carbonate tetramer and the hydroxide dimer are both characterized magnetically. Chapter 5 describes an unusual nitrile condensation by the 2Ni-2OH species characterized in Chapter 4. Urea, as well as dimethylurea and acetamide participate in this reaction, leading to an imidoylamidine nickel complex, which is crystallographically characterized. Finally chapter 6 describes four nickel complexes each containing an RDPA ligand species. 1:2 nickel:ligand complexes containing BzDPA and isopropyl-dipicolylamine (iPrDPA) are characterized, as well as two novel tBuDPA nickel complexes with different counterions. Nickel(II) chloride gives rise to an unusual 2Ni-3Cl dimer complex, which nickel(II) nitrate…

Subjects/Keywords: Chemistry; Inorganic

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APA (6^th Edition):

Wikstrom, J. P. (2009). Biomimetic dipicolylamine nickel complexes| Structure and reactivity. (Thesis). Tufts University. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=3379046

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Wikstrom, Jeffrey P. “Biomimetic dipicolylamine nickel complexes| Structure and reactivity.” 2009. Thesis, Tufts University. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=3379046.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Wikstrom, Jeffrey P. “Biomimetic dipicolylamine nickel complexes| Structure and reactivity.” 2009. Web. 23 Feb 2020.

Vancouver:

Wikstrom JP. Biomimetic dipicolylamine nickel complexes| Structure and reactivity. [Internet] [Thesis]. Tufts University; 2009. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3379046.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Wikstrom JP. Biomimetic dipicolylamine nickel complexes| Structure and reactivity. [Thesis]. Tufts University; 2009. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3379046

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

16. Seaman, Lani Anne. Investigation of the 6d and 5f Orbital Contributions in Actinide Complexes Containing Amide, Ketimide, Aryl, and Alkyl Metal-Ligand Bonds.

Degree: 2013, University of California, Santa Barbara

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=3545129

► Treatment of UCl₄ with 6 equiv of LiNH^tBu generates the U(IV) amide complex, {[Li(THF)₂Cl]₂[Li]₂[U(NH^tBu)₆]}_n in good yields. Oxidation of {[Li(THF)₂Cl]₂[Li]₂[U(NH^tBu)₆]}_n with… (more)

Subjects/Keywords: Chemistry; Inorganic

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APA (6^th Edition):

Seaman, L. A. (2013). Investigation of the 6d and 5f Orbital Contributions in Actinide Complexes Containing Amide, Ketimide, Aryl, and Alkyl Metal-Ligand Bonds. (Thesis). University of California, Santa Barbara. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=3545129

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Seaman, Lani Anne. “Investigation of the 6d and 5f Orbital Contributions in Actinide Complexes Containing Amide, Ketimide, Aryl, and Alkyl Metal-Ligand Bonds.” 2013. Thesis, University of California, Santa Barbara. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=3545129.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Seaman, Lani Anne. “Investigation of the 6d and 5f Orbital Contributions in Actinide Complexes Containing Amide, Ketimide, Aryl, and Alkyl Metal-Ligand Bonds.” 2013. Web. 23 Feb 2020.

Vancouver:

Seaman LA. Investigation of the 6d and 5f Orbital Contributions in Actinide Complexes Containing Amide, Ketimide, Aryl, and Alkyl Metal-Ligand Bonds. [Internet] [Thesis]. University of California, Santa Barbara; 2013. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3545129.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Seaman LA. Investigation of the 6d and 5f Orbital Contributions in Actinide Complexes Containing Amide, Ketimide, Aryl, and Alkyl Metal-Ligand Bonds. [Thesis]. University of California, Santa Barbara; 2013. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3545129

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

The University of Arizona

17. Jenkins, Judith Lynn. Spectroscopic and spectroelectrochemical characterization of fundamental interfacial charge transfer processes relevant to efficient solar energy conversion.

Degree: 2013, The University of Arizona

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=3546721

► Solar energy conversion is accomplished by multilayered devices consisting of various conducting and semiconducting materials. Because the layers are only 10s – 100s of… (more)

▼ Solar energy conversion is accomplished by multilayered devices consisting of various conducting and semiconducting materials. Because the layers are only 10s – 100s of nm thick, device behavior is governed primarily by interfacial molecular dynamics that often differ from the bulk behavior of these materials. The thermodynamics and kinetics of the interfacial interactions are particularly interesting, as interfacial electron transfer strongly influence the efficiency of photovoltaics and devices used in solar hydrogen production. This work focuses specifically on interfacial charge transfer processes occurring at three interfaces relevant to thin film organic/inorganic solar energy conversion devices. i) A potential-step polymer electrochemical deposition and doping procedure was developed and used to create poly(3-hexylthiophene) (e-P3HT) interlayer films for organic photovoltaics. Photoelectron spectroscopies suggest that an interface dipole forms spontaneously at the polymer donor/fullerene acceptor interface through partial interfacial charge transfer prior to photoexcitation; this doping-dependent interfacial dipole was correlated to the electrical properties of these critical heterojunctions. ii) Potential-modulated fluorescence spectroscopy (PMF) was developed and used examine the kinetics of the reversible oxidation of the (e-P3HT) films in attempt to elucidate the ITO/e-P3HT charge transfer rates. However, the optical switching increased linearly as the polymer film decreased, indicating that the molecular-level process probed by PMF was rate-limited by counter-ion movement into and out of the polymer film. iii) Potential-modulated attenuated total reflectance spectroscopy (PM-ATR) was used to examine the reversible reduction of CdSe semiconductor nanocrystals tethered to indium tin oxide electrodes as well as the surface-coverage dependent bleaching of these nanocrystals. A new equivalent circuit model describing the CdSe/ITO electrode is proposed, and a PM-ATR simulation program was used to quantify Faradiac resistances to interfacial charge transfer that trend with the magnitude of overpotential. The insights gained through these experiments add to a growing understanding of the fundamental, molecular-level competition between photoinduced charge generation and parasitic charge recombination at these critical interfaces.

Subjects/Keywords: Chemistry; Inorganic

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Jenkins, J. L. (2013). Spectroscopic and spectroelectrochemical characterization of fundamental interfacial charge transfer processes relevant to efficient solar energy conversion. (Thesis). The University of Arizona. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=3546721

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Jenkins, Judith Lynn. “Spectroscopic and spectroelectrochemical characterization of fundamental interfacial charge transfer processes relevant to efficient solar energy conversion.” 2013. Thesis, The University of Arizona. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=3546721.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Jenkins, Judith Lynn. “Spectroscopic and spectroelectrochemical characterization of fundamental interfacial charge transfer processes relevant to efficient solar energy conversion.” 2013. Web. 23 Feb 2020.

Vancouver:

Jenkins JL. Spectroscopic and spectroelectrochemical characterization of fundamental interfacial charge transfer processes relevant to efficient solar energy conversion. [Internet] [Thesis]. The University of Arizona; 2013. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3546721.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Jenkins JL. Spectroscopic and spectroelectrochemical characterization of fundamental interfacial charge transfer processes relevant to efficient solar energy conversion. [Thesis]. The University of Arizona; 2013. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3546721

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

18. Hurst, Sarah Jean. "Three-dimensional hybridization" with polyvalent DNA-gold nanoparticle conjugates.

Degree: 2009, Northwestern University

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=3352623

► It is clear that remarkable progress has been made in understanding the fundamental properties of and potential applications for polyvalent DNA-gold nanoparticle conjugates (Chapter… (more)

▼ It is clear that remarkable progress has been made in understanding the fundamental properties of and potential applications for polyvalent DNA-gold nanoparticle conjugates (Chapter 1). Many important questions have been answered yet many still remain. The work presented in this dissertation will delve into several of these issues. In Chapter 2, methods are outlined that can be used to finely tune the DNA density on the surface of gold nanoparticles ranging from 15 to 250 nm in diameter. Until this study, the experimental parameters that could be used to maximize DNA loading on the surface of gold nanoparticles were not well understood and a reliable protocol for functionalizing gold nanoparticles up to 250 nm in diameter with a high density of DNA did not exist. Using the protocols presented in these studies, a series of DNA-gold nanoparticle probes with a range of valencies, particle sizes, and DNA compositions were synthesized and the effect of such architectural modifications on the cooperative properties of these structures were explored, particularly in terms of elucidating and controlling the nature of their “three-dimensional hybridization” to form nanoparticle aggregate structures (Chapters 3 and 4). These studies also allowed comparisons to be drawn between the stability of free duplex DNA and duplex DNA immobilized on the nanoparticle surface. The results obtained in these investigations are of textbook importance in understanding the fundamental behavior of nanoscale systems, but also serve a practical purpose. These principles can be used to precisely and dependably tailor the architecture (and as a result the properties) of DNA-Au NP conjugates to fit a specific purpose in a given application. For instance, Chapter 5 highlights a DNA-Au NP-based, colorimetric scheme, that relies on nanoparticle hybridization events, that can be used to determine the selectivity of DNA binding molecules for particular sequences of DNA. Finally, Chapter 6 presents a short summary of the advances enabled by this work and provides insight into ways these topics can be moved forward in the future both in the fundamental and applied realms.

Subjects/Keywords: Chemistry; Inorganic

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APA (6^th Edition):

Hurst, S. J. (2009). "Three-dimensional hybridization" with polyvalent DNA-gold nanoparticle conjugates. (Thesis). Northwestern University. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=3352623

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Hurst, Sarah Jean. “"Three-dimensional hybridization" with polyvalent DNA-gold nanoparticle conjugates.” 2009. Thesis, Northwestern University. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=3352623.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Hurst, Sarah Jean. “"Three-dimensional hybridization" with polyvalent DNA-gold nanoparticle conjugates.” 2009. Web. 23 Feb 2020.

Vancouver:

Hurst SJ. "Three-dimensional hybridization" with polyvalent DNA-gold nanoparticle conjugates. [Internet] [Thesis]. Northwestern University; 2009. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3352623.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Hurst SJ. "Three-dimensional hybridization" with polyvalent DNA-gold nanoparticle conjugates. [Thesis]. Northwestern University; 2009. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3352623

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Southern California

19. Hanson, Kenneth. Synthesis, photophysical and electrochemical characterization of 1,3-bis(2-pyridylimino)isoindole derivatives.

Degree: 2010, University of Southern California

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=3418255

► The light emitting and absorbing small molecules are interesting for many applications ranging from solar energy conversion to photodynamic therapy. There are many variables… (more)

▼ The light emitting and absorbing small molecules are interesting for many applications ranging from solar energy conversion to photodynamic therapy. There are many variables that contribute to the intensity, energy and efficiency of absorption and emission including the HOMO/LUMO energy levels, molar absorptivities, excited state lifetimes, geometry changes in the excited state, radiative and nonradiative rates, and others. One of the fundamental goals of photophysical chemists is to understand how molecular structure correlates with these properties. Once structure-property relationships are understood, new molecules can be designed with particular applications in mind. In this thesis, the synthesis, electrochemical and photophysical properties 1,3-bis(2-pyridylimino)isoindoline (BPI) derivatives will be reported and structure property relationships discussed. In chapter one general concepts and nomenclature associated with the photophysics of small molecules are introduced. The discussion begins with the simplest of light absorbing materials, hydrogen, and then expands to many electron, molecular systems. Prior to discussing the photophysical properties of BPI derivatives, the synthesis of both the BPI based molecules and platinum BPI complexes will be described in chapter two. To confirm the identity of the compounds all products were characterized by mass spectrometry, x-ray crystallography, elemental analysis and NMR spectroscopy. Although the parent BPI is non-emissive at room temperature, fluorescence from the dihydroxy substituted BPI derivatives is discussed in chapter 3. The unusual emission from these compounds is attributed to an excited state proton transfer as supported by the large apparent Stokes shift (6600 cm −1) between absorption and emission, the lack of emission from the alkoxy substituted BPI and the large changes in lifetime/efficiency in deauterated methanol (MeOD). In chapter four, the photophysical and electrochemical characterization of a series of platinum(II) complexes of the form (N N N)PtX where N N N isan assortment of substituted 1,3-bis(2-pyridylimino)isoindolate ligands and X represents various anionic monodentate ligands is discussed. It has been found that the quantum efficiency of emission for all of the complexes is dictated by the nonradiative rates of deactivation from the excited state. The nonradiative rates of the platinum chloride complexes are found to correlate with the energy gap law. For other PtX complexes the graph of the natural log of the nonradiative rates versus energy of emission was found to be nonlinear. The nature of these nonradiative processes is investigated from temperature dependent studies on the excited state lifetime. Finally, in chapter five a series of five platinum(II) chloride BPI based complexes with varying degrees of benzanulation are characterized. For this series of molecules, either a blue shift or a red shift in absorption and emission maxima,…

Subjects/Keywords: Chemistry; Inorganic

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APA (6^th Edition):

Hanson, K. (2010). Synthesis, photophysical and electrochemical characterization of 1,3-bis(2-pyridylimino)isoindole derivatives. (Thesis). University of Southern California. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=3418255

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Hanson, Kenneth. “Synthesis, photophysical and electrochemical characterization of 1,3-bis(2-pyridylimino)isoindole derivatives.” 2010. Thesis, University of Southern California. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=3418255.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Hanson, Kenneth. “Synthesis, photophysical and electrochemical characterization of 1,3-bis(2-pyridylimino)isoindole derivatives.” 2010. Web. 23 Feb 2020.

Vancouver:

Hanson K. Synthesis, photophysical and electrochemical characterization of 1,3-bis(2-pyridylimino)isoindole derivatives. [Internet] [Thesis]. University of Southern California; 2010. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3418255.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Hanson K. Synthesis, photophysical and electrochemical characterization of 1,3-bis(2-pyridylimino)isoindole derivatives. [Thesis]. University of Southern California; 2010. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3418255

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Washington

20. Manner, Virginia W. Concerted proton-electron transfer reactions of ruthenium and cobalt complexes| Studies on distance dependence and spin effects.

Degree: 2010, University of Washington

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=3370598

► Coupling electron transfer to proton transfer is key to converting solar energy to chemical fuels, and more generally in a wide range of chemical… (more)

▼ Coupling electron transfer to proton transfer is key to converting solar energy to chemical fuels, and more generally in a wide range of chemical and biochemical processes. Although electron transfers have been thoroughly studied over many decades, the fundamentals of proton-coupled electron transfer (PCET) are still being worked out. In order to understand how the distance between the electron and proton-accepting sites affects PCET, this dissertation focuses on the preparation and reactivity of Ru complexes with large separations between the redox-active metal and the basic carboxylate site. The Ru(III) complex, Ru^III(pydic)(terpy-COO) (Ru^IIICOO), has been isolated with a terpyridine-4'-carboxylate ligand, in which there are six bonds and 6.9 Å between the redox-active Ru and the basic carboxylate. Ru^IIICOO oxidizes substrates by removal of e− and H⁺ to form the protonated Ru(II) complex, Ru^IICOOH. Thermochemical analyses indicate that these reactions occur by concerted transfer of the proton and electron despite the large distance between the Ru and the H⁺-accepting oxygen. To further understand how the reactivity has been affected by this distance, the separation between the Ru and basic site has been increased by inserting a phenyl group between the terpyridine and the carboxylate in the analogous Ru(III) complex, Ru^IIIPhCOO. Even with this separation, Ru^IIIPhCOO also oxidizes hydrogen atom donors X-H in a concerted (CPET) process, although the reactions typically proceed more slowly than in the system without the phenyl spacer. The large distance between the metal and carboxylate sites in both systems appears to complicate the patterns of reactivity, so that simple treatments, such as linear free energy relationships and Marcus Theory, do not explain the observed trends. This is the first study to address the distance dependence of the proton and electron accepting sites in PCET reactivity, and has important implications for systems where long distance electron transfer is coupled to proton transfer. A separate project involving PCET with cobalt biimidazoline complexes is also presented. The low-spin Co(III) complex, Co^IIIHbim, reacts with hydrogen atom donors to form high-spin Co^IIH₂bim in a CPET process. This system also deviates from typical Marcus behavior, which is likely due to the change in spin state that occurs during reactivity.

Subjects/Keywords: Chemistry; Inorganic

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Manner, V. W. (2010). Concerted proton-electron transfer reactions of ruthenium and cobalt complexes| Studies on distance dependence and spin effects. (Thesis). University of Washington. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=3370598

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Manner, Virginia W. “Concerted proton-electron transfer reactions of ruthenium and cobalt complexes| Studies on distance dependence and spin effects.” 2010. Thesis, University of Washington. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=3370598.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Manner, Virginia W. “Concerted proton-electron transfer reactions of ruthenium and cobalt complexes| Studies on distance dependence and spin effects.” 2010. Web. 23 Feb 2020.

Vancouver:

Manner VW. Concerted proton-electron transfer reactions of ruthenium and cobalt complexes| Studies on distance dependence and spin effects. [Internet] [Thesis]. University of Washington; 2010. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3370598.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Manner VW. Concerted proton-electron transfer reactions of ruthenium and cobalt complexes| Studies on distance dependence and spin effects. [Thesis]. University of Washington; 2010. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3370598

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

21. Hoel, Cathleen Ann. Polymorphism and Local Structure of Crystalline and Amorphous Zinc-Indium-Tin Oxide (ZITO).

Degree: 2011, Northwestern University

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=3433582

► The transparent conducting oxide (TCO) and co-substituted solid solution In_2-2xZn_xSn_xO₃ (ZITO) has gained attention as a replacement for the industry standard Sn-doped In₂O₃… (more)

▼ The transparent conducting oxide (TCO) and co-substituted solid solution In_2-2xZn_xSn_xO₃ (ZITO) has gained attention as a replacement for the industry standard Sn-doped In₂O₃ (ITO). Ambient pressure bixbyite and high-pressure corundum ZITO, both crystalline phases, and metastable and amorphous ZITO were synthesized and their local structures were investigated. The short-range structures of the crystalline phases, bixbyite and corundum ZITO, were probed to develop a basis for understanding the short-range structure of amorphous ZITO. The bixbyite structure type (x ≤ 0.4), the most stable phase, was synthesized by solid state reaction in air. Corundum ZITO (x ≤ 0.7), which was first synthesized during the course of this work, was made by high-pressure solid state reaction, by calcination of crystalline oxyhydroxide and hydroxide precursors, and by growth of epitaxial thin films using pulsed-laser deposition. Amorphous ZITO was synthesized by coprecipitation, drying (80 °C) and calcination (300 °C). Both the bixbyite and corundum solid solutions exhibit, as expected, decreasing lattice constants with increasing substitution of the smaller zinc and tin cations. Extended X-ray absorption fine structure (EXAFS) of bixbyite and corundum ZITO revealed that the Zn and Sn local coordination environments remain pseudo-octahedral and that these two ions remain as near metal neighbors at a Zn-Sn distance of ~3.2 Å in corundum. The structure of amorphous ZITO was examined in detail by X-ray diffraction, electron nanodiffraction, total X-ray scattering and X-ray absorption spectroscopy. The structural units present in amorphous ZITO were InO₆, SnO₆ and ZnO₄ in contrast to the bixbyite and corundum structure types where the basic structural units are all pseudo-octahedral. The In-O, Sn-O and Zn-O bond lengths in amorphous ZITO were all different to owing to the different cationic radii for indium, tin and zinc. The use of mild synthesis conditions favored the formation of tetrahedral ZnO₄ with the consequence that crystallization was inhibited. This work shows how the method of synthesis, and the individual cationic radii and charges of indium, zinc and tin, together influence the local and extended structure of In_2-2xZn_xSn_xO₃.

Subjects/Keywords: Chemistry; Inorganic

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Hoel, C. A. (2011). Polymorphism and Local Structure of Crystalline and Amorphous Zinc-Indium-Tin Oxide (ZITO). (Thesis). Northwestern University. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=3433582

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Hoel, Cathleen Ann. “Polymorphism and Local Structure of Crystalline and Amorphous Zinc-Indium-Tin Oxide (ZITO).” 2011. Thesis, Northwestern University. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=3433582.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Hoel, Cathleen Ann. “Polymorphism and Local Structure of Crystalline and Amorphous Zinc-Indium-Tin Oxide (ZITO).” 2011. Web. 23 Feb 2020.

Vancouver:

Hoel CA. Polymorphism and Local Structure of Crystalline and Amorphous Zinc-Indium-Tin Oxide (ZITO). [Internet] [Thesis]. Northwestern University; 2011. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3433582.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Hoel CA. Polymorphism and Local Structure of Crystalline and Amorphous Zinc-Indium-Tin Oxide (ZITO). [Thesis]. Northwestern University; 2011. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3433582

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Harvard University

22. Koo, Bon Jun. The Development and Analysis of Model Systems to Probe Proton-Coupled Electron Transfer in Ribonucleotide Reductase Ia of E. Coli.

Degree: PhD, 2016, Harvard University

URL: http://nrs.harvard.edu/urn-3:HUL.InstRepos:33493539

►

Proton-coupled electron transfer (PCET) combines proton transfer with electron transfer to bypass high-energy intermediates. The ribonucleotide reductase (RNR) family of enzymes catalyzes the conversion of… (more)

▼

Proton-coupled electron transfer (PCET) combines proton transfer with electron transfer to bypass high-energy intermediates. The ribonucleotide reductase (RNR) family of enzymes catalyzes the conversion of ribonucleotides to deoxynucleotides using amino acid radicals. The enzyme contains an efficient PCET pathway that transfers an electron and proton over a 35 Å distance across two subunits, the longest PCET pathway known in biology. The enzyme func-tions with very high fidelity, performing >105 turnovers before radical loss. This thesis explores PCET in model systems to understand the radical transport pathway in E. coli RNR type Ia. First, amino acid radical generation was explored by laser spectroscopy. Small molecule systems, where photooxidants were appended with amino acids, provide a plat-form for probing both the pH and driving force dependence of PCET. Analysis of the emission kinetics of these systems indicate that amino acid radicals were generated by sequential electron and proton transfers as a result of the strong driving force of the photooxidant. Next, the dyad model with cofacial aromatic units was developed to investigate the PCET radical transport mechanism between two adjacent amino acids. Inspired by the unique redox cooperativity ob-served in Y730-Y731 tyrosine dyads at the α2β2 interface of RNR, electrochemical and computa-tional approaches were used to probe the correlation between the structural and redox properties of the dyad model. Using electrochemical and computational analysis, it was determined that the presence of two phenol units in the dyad lowered the reduction potential by ~ 60 mV. This result demonstrates that the tyrosine dyad behaves as a discrete redox unit, consistent with the observed radical transport pathway observed in RNR. Finally, the bidirectional PCET pathway in the β2 subunit of RNR (Y122-W48-Y356) was modeled using a polyproline-based peptide. The long-distance electron transfer between tyrosine analogs and tryptophan was investigated by pulse ra-diolysis to determine the radical transfer rate in these peptide models. Since efficient electron transfer was observed between tetrafluorotyrosine and tryptophan at a 10 Å distance in the model system, Y122 and W48 at a 7.4 Å distance in RNR likely serve as the radical transport pathway in a bidirectional, sequential electron and proton transfer mechanism.

Chemistry and Chemical Biology

Advisors/Committee Members: Nocera, Daniel G. xmlui.authority.confidence.description.cf_uncertain (advisor), Stubbe, JoAnne (committee member), Kahne, Daniel E. (committee member).

Subjects/Keywords: Chemistry; Inorganic

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Koo, B. J. (2016). The Development and Analysis of Model Systems to Probe Proton-Coupled Electron Transfer in Ribonucleotide Reductase Ia of E. Coli. (Doctoral Dissertation). Harvard University. Retrieved from http://nrs.harvard.edu/urn-3:HUL.InstRepos:33493539

Chicago Manual of Style (16^th Edition):

Koo, Bon Jun. “The Development and Analysis of Model Systems to Probe Proton-Coupled Electron Transfer in Ribonucleotide Reductase Ia of E. Coli.” 2016. Doctoral Dissertation, Harvard University. Accessed February 23, 2020. http://nrs.harvard.edu/urn-3:HUL.InstRepos:33493539.

MLA Handbook (7^th Edition):

Koo, Bon Jun. “The Development and Analysis of Model Systems to Probe Proton-Coupled Electron Transfer in Ribonucleotide Reductase Ia of E. Coli.” 2016. Web. 23 Feb 2020.

Vancouver:

Koo BJ. The Development and Analysis of Model Systems to Probe Proton-Coupled Electron Transfer in Ribonucleotide Reductase Ia of E. Coli. [Internet] [Doctoral dissertation]. Harvard University; 2016. [cited 2020 Feb 23]. Available from: http://nrs.harvard.edu/urn-3:HUL.InstRepos:33493539.

Council of Science Editors:

Koo BJ. The Development and Analysis of Model Systems to Probe Proton-Coupled Electron Transfer in Ribonucleotide Reductase Ia of E. Coli. [Doctoral Dissertation]. Harvard University; 2016. Available from: http://nrs.harvard.edu/urn-3:HUL.InstRepos:33493539

Yale University

23. Bielinski, Elizabeth Anne. Transition Metal Catalysts for Hydrogen Storage and Carbon Dioxide Activation.

Degree: 2015, Yale University

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=3663448

► This dissertation describes the synthesis of a series of transition metal compounds and their reactivity with hydrogen and carbon dioxide for application in reversible… (more)

Subjects/Keywords: Inorganic chemistry

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APA (6^th Edition):

Bielinski, E. A. (2015). Transition Metal Catalysts for Hydrogen Storage and Carbon Dioxide Activation. (Thesis). Yale University. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=3663448

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Bielinski, Elizabeth Anne. “Transition Metal Catalysts for Hydrogen Storage and Carbon Dioxide Activation.” 2015. Thesis, Yale University. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=3663448.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Bielinski, Elizabeth Anne. “Transition Metal Catalysts for Hydrogen Storage and Carbon Dioxide Activation.” 2015. Web. 23 Feb 2020.

Vancouver:

Bielinski EA. Transition Metal Catalysts for Hydrogen Storage and Carbon Dioxide Activation. [Internet] [Thesis]. Yale University; 2015. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3663448.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Bielinski EA. Transition Metal Catalysts for Hydrogen Storage and Carbon Dioxide Activation. [Thesis]. Yale University; 2015. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3663448

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

24. Hamaed, Ahmad. Hydrogen Storage in Metal Fragments grafted Silicas and Chromium Hydrazide Gels.

Degree: PhD, Chemistry and Biochemistry, 2010, National Library of Canada

URL: http://scholar.uwindsor.ca/etd/392

► Hexagonally-packed mesoporous silicas (HMS) grafted with low-valent titanium, vanadium, and chromium organometallic fragments possessing oxidation states between (II) and (IV) were synthesized, tested for their… (more)

▼ Hexagonally-packed mesoporous silicas (HMS) grafted with low-valent titanium, vanadium, and chromium organometallic fragments possessing oxidation states between (II) and (IV) were synthesized, tested for their hydrogen storage capacities, and characterized by XRD, nitrogen adsorption, XPS, and EA. The effects of the variation in the surface area, pore size, transition metal type, and metal oxidation state, the organometallic loading levels, as well as the ligand environment on the H2 adsorption capacity and the binding enthalpies of these systems were investigated. This study demonstrated that titanium is more effective at hydrogen binding than vanadium and chromium. HMS silica grafted with benzyl titanium (III) fragments can accommodate up to 4.85 H2 per Ti center. This compares to 2.74 H2 per vanadium center as for the HMS grafted with tris(mesityl) vanadium, and to 1.82 and 2.20 H2 per chromium as for the HMS treated with the tris[bis(trimethylsilyl)methyl] chromium and bis[(trimethylsilyl)methyl]chromium respectively. The hydrogenation of the metal centers had a pronounced effect on the adsorption capacity of the Cr-grafted HMS. This capacity increased from 1.82 to 3.20 H2 per chromium in the case of HMS treated with tris[bis(trimethylsilyl)methyl] chromium, and from 2.20 H2 to 3.50 H2 per chromium in the case of HMS treated with tris[(trimethylsilyl)methyl] chromium. The investigated systems in the first part were used as modules in the design of novel chromium hydrazide gels that use low valent chromium centers as H2 binding sites. These materials were synthesized at various Cr to hydrazine molar ratios and have room temperature excess hydrogen storage of up to 1.01 wt%, and binding enthalpy of up to viii 22.9 kJ/mol. However, the hydrogenation of these materials induced an amplification of the performance and binding enthalpies. The excess room temperature hydrogen storage of the hydrogenated samples goes up to 1.65 wt%, with the room absolute volumetric density goes up to 29.92 Kg/m3, and with binding enthalpy goes up to 51.59 kJ/mol. These materials would use pressure instead of temperature as a toggle and can thus be used in compressed gas tanks, to increase the amount of hydrogen stored, and therefore the driving range of any vehicle. Advisors/Committee Members: Antonelli, David (Chemistry and Biochemistry).

Subjects/Keywords: Chemistry; Inorganic.

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APA (6^th Edition):

Hamaed, A. (2010). Hydrogen Storage in Metal Fragments grafted Silicas and Chromium Hydrazide Gels. (Doctoral Dissertation). National Library of Canada. Retrieved from http://scholar.uwindsor.ca/etd/392

Chicago Manual of Style (16^th Edition):

Hamaed, Ahmad. “Hydrogen Storage in Metal Fragments grafted Silicas and Chromium Hydrazide Gels.” 2010. Doctoral Dissertation, National Library of Canada. Accessed February 23, 2020. http://scholar.uwindsor.ca/etd/392.

MLA Handbook (7^th Edition):

Hamaed, Ahmad. “Hydrogen Storage in Metal Fragments grafted Silicas and Chromium Hydrazide Gels.” 2010. Web. 23 Feb 2020.

Vancouver:

Hamaed A. Hydrogen Storage in Metal Fragments grafted Silicas and Chromium Hydrazide Gels. [Internet] [Doctoral dissertation]. National Library of Canada; 2010. [cited 2020 Feb 23]. Available from: http://scholar.uwindsor.ca/etd/392.

Council of Science Editors:

Hamaed A. Hydrogen Storage in Metal Fragments grafted Silicas and Chromium Hydrazide Gels. [Doctoral Dissertation]. National Library of Canada; 2010. Available from: http://scholar.uwindsor.ca/etd/392

Temple University

25. Imler, Gregory H. Reactivity, Characterization, Equilibrium Thermodynamics and Hetero-bimetallic Studies of Tridentate and Tetradentate Complexes Relevant to Syngas Catalysis.

Degree: PhD, 2014, Temple University

URL: http://digital.library.temple.edu/u?/p245801coll10,302256

►

Chemistry

The unifying objective of this work is the study of model systems that will assist in the development of new metal catalysts capable of… (more)

▼

Chemistry

The unifying objective of this work is the study of model systems that will assist in the development of new metal catalysts capable of converting carbon monoxide and hydrogen (syngas) into organic oxygenates at mild temperature and pressure. The selective catalytic transformation of carbon monoxide and hydrogen to liquid fuels and chemical feedstocks represents a major "Grand Challenge" of catalysis science. A core objective is the study of a macrocycle that is related to a porphyrin ligand in order to circumvent some of the disadvantages of utilizing porphyrins in catalysis. The rhodium complex of the macrocycle dibenzotetramethylaza[14]annulene ([(tmtaa)Rh]2]) was reacted with a series of small molecules relevant to CO reduction and hydrogenation. Several complexes were formed that demonstrated the ability to partially reduce and hydrogenate carbon monoxide, including the dirhodium ketone (Rh-C(O)-Rh) and an example of a thermodynamically favorable metal formyl complex ((tmtaa)Rh-C(O)H). An important feature of this work is the measurement of thermodynamic data to provide experimental benchmarks for obtaining key species in CO reduction and hydrogenation. A thorough study of the (tmtaa)Rh system will help in identifying structural features that assist or hinder CO hydrogenation. All reactions are monitored by 1H NMR which permits determination of solution thermodynamics from equilibrium constants obtained by NMR peak integrations. DFT calculations have supplemented experimental results by providing estimates to compare with the experimentally determined thermodynamic data. These computations also provide insight into the structures and thermodynamics of species that cannot be observed directly such as short lived intermediates and thermodynamically unfavorable products. Heterobimetallic complexes of (tmtaa)Rh* with a second metal radical have been utilized to attempt to convert CO to organic products. Reactivity with CO and H2 has been accomplished, with most of these metal systems providing (tmtaa)Rh-C(O)H and M-H as final products. These systems are now ideally set up for catalysis in which M-H can deliver hydrogen to reduce and hydrogenate the rhodium formyl unit. Performing these reactions at high pressures of CO/H2 or with a more sterically hindered analog of tmtaa may provide the conditions necessary for catalysis. Reactivity, thermodynamic and computational studies have been used to analyze and compare bond energies in this current work with previous studies accomplished in the Wayland group. These comparisons permit further understanding into the factors that control bond strength, guiding future studies and allowing tuning of bond strengths based on choice of conditions for a catalytic process. This research has resulted in a more complete understanding of the factors that control the favorability of various intermediates in CO reduction and hydrogenation and the application of these results can be used to guide the next generation of metal ligand systems that will yield organic…

Advisors/Committee Members: Wayland, Bradford B.;, Zdilla, Michael J., Valentine, Ann M., Cannon, Kevin C.;.

Subjects/Keywords: Inorganic chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Imler, G. H. (2014). Reactivity, Characterization, Equilibrium Thermodynamics and Hetero-bimetallic Studies of Tridentate and Tetradentate Complexes Relevant to Syngas Catalysis. (Doctoral Dissertation). Temple University. Retrieved from http://digital.library.temple.edu/u?/p245801coll10,302256

Chicago Manual of Style (16^th Edition):

Imler, Gregory H. “Reactivity, Characterization, Equilibrium Thermodynamics and Hetero-bimetallic Studies of Tridentate and Tetradentate Complexes Relevant to Syngas Catalysis.” 2014. Doctoral Dissertation, Temple University. Accessed February 23, 2020. http://digital.library.temple.edu/u?/p245801coll10,302256.

MLA Handbook (7^th Edition):

Imler, Gregory H. “Reactivity, Characterization, Equilibrium Thermodynamics and Hetero-bimetallic Studies of Tridentate and Tetradentate Complexes Relevant to Syngas Catalysis.” 2014. Web. 23 Feb 2020.

Vancouver:

Imler GH. Reactivity, Characterization, Equilibrium Thermodynamics and Hetero-bimetallic Studies of Tridentate and Tetradentate Complexes Relevant to Syngas Catalysis. [Internet] [Doctoral dissertation]. Temple University; 2014. [cited 2020 Feb 23]. Available from: http://digital.library.temple.edu/u?/p245801coll10,302256.

Council of Science Editors:

Imler GH. Reactivity, Characterization, Equilibrium Thermodynamics and Hetero-bimetallic Studies of Tridentate and Tetradentate Complexes Relevant to Syngas Catalysis. [Doctoral Dissertation]. Temple University; 2014. Available from: http://digital.library.temple.edu/u?/p245801coll10,302256

26. Baus, Jacob. Synthesis and Characterization of Iron(II) Complexes Modeling the Active Site Structure of Nonheme Iron Dioxygenases.

Degree: 2012, Marquette University

URL: https://epublications.marquette.edu/theses_open/134

► The aerobic degradation of polycyclic aromatic compounds, which are widespread contaminants in soils and groundwaters, is carried-out in large part by various Fe-containing dioxygenases that… (more)

Subjects/Keywords: Inorganic Chemistry

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APA (6^th Edition):

Baus, J. (2012). Synthesis and Characterization of Iron(II) Complexes Modeling the Active Site Structure of Nonheme Iron Dioxygenases. (Thesis). Marquette University. Retrieved from https://epublications.marquette.edu/theses_open/134

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Baus, Jacob. “Synthesis and Characterization of Iron(II) Complexes Modeling the Active Site Structure of Nonheme Iron Dioxygenases.” 2012. Thesis, Marquette University. Accessed February 23, 2020. https://epublications.marquette.edu/theses_open/134.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Baus, Jacob. “Synthesis and Characterization of Iron(II) Complexes Modeling the Active Site Structure of Nonheme Iron Dioxygenases.” 2012. Web. 23 Feb 2020.

Vancouver:

Baus J. Synthesis and Characterization of Iron(II) Complexes Modeling the Active Site Structure of Nonheme Iron Dioxygenases. [Internet] [Thesis]. Marquette University; 2012. [cited 2020 Feb 23]. Available from: https://epublications.marquette.edu/theses_open/134.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Baus J. Synthesis and Characterization of Iron(II) Complexes Modeling the Active Site Structure of Nonheme Iron Dioxygenases. [Thesis]. Marquette University; 2012. Available from: https://epublications.marquette.edu/theses_open/134

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Temple University

27. Gau, Michael. Self-assembled, labile, multinuclear metal complexes inspired by nature's oxygen-evolving complex of photosystem II and iron-molybdenum cofactor.

Degree: PhD, 2017, Temple University

URL: http://digital.library.temple.edu/u?/p245801coll10,430413

►

Chemistry

The aim of this work is to synthesize and study novel multinuclear manganese systems to model the structure and function of the oxygen-evolving complex… (more)

▼

Chemistry

The aim of this work is to synthesize and study novel multinuclear manganese systems to model the structure and function of the oxygen-evolving complex (OEC). With the synthesis and study of these model complexes, a greater understanding of nature’s OEC mechanism and processes will come to fruition as well as a viable homogenous water-oxidation catalyst. In addition, small molecule activation was investigated using an FeI precursor. A tetramanganese “pinned-butterfly” cluster with the chemical formula Mn4(µ3-N2Ph2)2(µ-N2Ph2)(µ-NHPh)2(L)4, was synthesized via self-assembly with the addition of N, N’-diphenylhydrazine to Mn(N(SiMe3)2)2). The reaction proceeds over the course of a few hours with a visible color change pale yellow to yellow, black and finally red. The self-assembly mechanism was elucidated with methods such as ligand labeling, kinetic isotope effect, IR spectroscopy, X-ray diffractometry (single crystal and powder), UV/vis kinetic studies and absorbance studies, hydrogen-atom transfer (HAT) competition studies, NMR studies, GC studies and freezing point depression studies. The “twisted basket” cluster is a two-hydrogen-atom reduced analogue of the aforementioned “pinned-butterfly” cluster with a chemical formula of Mn4(µ-NHPh)4(µ-PhNNPh-2N,N’)2(py)4. Conversion between the clusters was investigated and achieved with the addition of an equivalent of N,N’-diphenylhydrazine and heat to a solution of the “pinned-butterfly” complex. This conversion between the clusters displays similarities to the OEC in the sense that it is undergoing proton-coupled electron transfer (PCET), cluster rearrangement and N-N bond formation. While these novel tetramanganese clusters provide us unique, reactive, and flexible clusters, they are far too sensitive to air and water to perform any useful catalysis. Due to the ligands’ lack of stabilization, alternate ligand platforms were investigated that would be able to form more rigid complexes, but retain lability. Bi- and tridentate ligands were investigated that resulted in the synthesis of several novel multinuclear homo- and hetero- metallic complexes. The ligands include polyoligimeric silsesquioxanes and substituted pyridines. These multinuclear Mn clusters show similarities to the OEC in their composition and structures. Upon exposure to air, a color change is observed without the precipitation of a manganese oxide insoluble species. This observation supports the increased stability, yet retained reactivity of the chelated clusters. Lastly, an FeI precursor was reacted with CS2 in attempts to isolate an Fe-S carbide complex and model the iron-molybdenum cofactor (FeMoco). Instead, a CS2 bridging dimer was formed and isolated. The activation of CS2 led us to attempt the reaction of the FeI precursor with other analogues such as CO2, diisopropylcarbodiimide, methylisothiocyanate, and phenylacetylene. CO2 and acetylene have been shown to be reactive substrates to the native FeMoco. These small molecule activated Fe complexes were characterized using X-ray…

Advisors/Committee Members: Zdilla, Michael J.;, Valentine, Ann M., Dobereiner, Graham, Marcum-Dietrich, Nanette;.

Subjects/Keywords: Inorganic chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Gau, M. (2017). Self-assembled, labile, multinuclear metal complexes inspired by nature's oxygen-evolving complex of photosystem II and iron-molybdenum cofactor. (Doctoral Dissertation). Temple University. Retrieved from http://digital.library.temple.edu/u?/p245801coll10,430413

Chicago Manual of Style (16^th Edition):

Gau, Michael. “Self-assembled, labile, multinuclear metal complexes inspired by nature's oxygen-evolving complex of photosystem II and iron-molybdenum cofactor.” 2017. Doctoral Dissertation, Temple University. Accessed February 23, 2020. http://digital.library.temple.edu/u?/p245801coll10,430413.

MLA Handbook (7^th Edition):

Gau, Michael. “Self-assembled, labile, multinuclear metal complexes inspired by nature's oxygen-evolving complex of photosystem II and iron-molybdenum cofactor.” 2017. Web. 23 Feb 2020.

Vancouver:

Gau M. Self-assembled, labile, multinuclear metal complexes inspired by nature's oxygen-evolving complex of photosystem II and iron-molybdenum cofactor. [Internet] [Doctoral dissertation]. Temple University; 2017. [cited 2020 Feb 23]. Available from: http://digital.library.temple.edu/u?/p245801coll10,430413.

Council of Science Editors:

Gau M. Self-assembled, labile, multinuclear metal complexes inspired by nature's oxygen-evolving complex of photosystem II and iron-molybdenum cofactor. [Doctoral Dissertation]. Temple University; 2017. Available from: http://digital.library.temple.edu/u?/p245801coll10,430413

28. Mogili, Sravya. Sol-Gel Synthesis of Aluminosilicate Glasses.

Degree: 2015, Southern Illinois University at Edwardsville

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=1584733

► The main goal of this research project is to synthesize aluminosilicate glass materials that are doped with praseodymium. To be useful for optical studies,… (more)

Subjects/Keywords: Chemistry; Inorganic

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APA (6^th Edition):

Mogili, S. (2015). Sol-Gel Synthesis of Aluminosilicate Glasses. (Thesis). Southern Illinois University at Edwardsville. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=1584733

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Mogili, Sravya. “Sol-Gel Synthesis of Aluminosilicate Glasses.” 2015. Thesis, Southern Illinois University at Edwardsville. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=1584733.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Mogili, Sravya. “Sol-Gel Synthesis of Aluminosilicate Glasses.” 2015. Web. 23 Feb 2020.

Vancouver:

Mogili S. Sol-Gel Synthesis of Aluminosilicate Glasses. [Internet] [Thesis]. Southern Illinois University at Edwardsville; 2015. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=1584733.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Mogili S. Sol-Gel Synthesis of Aluminosilicate Glasses. [Thesis]. Southern Illinois University at Edwardsville; 2015. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=1584733

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

29. Bittner, Michael M. Investigations of synthetic models of mononuclear nonheme iron dioxygenases.

Degree: 2014, Marquette University

URL: http://pqdtopen.proquest.com/#viewpdf?dispub=3642714

► Ring cleaving dioxygenases, such as o-aminophenol dioxygenase (APDO) and extradiol catechol dioxygenases (CatD), play an important role in human metabolism and the degradation of… (more)

▼ Ring cleaving dioxygenases, such as o-aminophenol dioxygenase (APDO) and extradiol catechol dioxygenases (CatD), play an important role in human metabolism and the degradation of aromatic pollutants, yet questions still remain concerning the enzymatic mechanisms. One area of the catalytic cycle that remains controversial is the geometric and electronic structure of the intermediate formed after O₂ binding to the Fe(II) centers. Synthetic model systems can be useful for studying enzyme active sites, as they are easier to modify and characterize than the enzymes themselves. However, synthetic models of APDOs have been relatively rare thus far. We prepared several monoiron(II) complexes that faithfully model the enzyme-substrate intermediates of o-aminophenol dioxygenases (APDO) and catechol dioxygenases. The complexes use either the ^Ph2Tp (^Ph2Tp = hydrotris(3,5-diphenylpyrazol-1-yl)borate) or ^Ph2TIP (^Ph2TIP = tris(4,5-diphenyl-1-methylimidazole)phosphine) supporting ligands and one of three bidentate, redox-active ligands: 4- tert-butylcatecholate, 4,6-di-tert-butyl-2-aminophenolate, or 4-tert-butyl-1,2-phenylenediamine. These complexes have been extensively characterized with crystallographic, spectroscopic, and electrochemical techniques, in conjunction with computational methods (e.g, density functional theory). Each complex is reactive towards O₂, and the geometric and electronic structures of the resulting species were examined with various methods to determine whether the oxidation is iron-based, ligand-based, or a combination of both. Treatment of the ^Ph2Tp ^Ph2TIP monoiron(II) aminophenolate complex with a phenoxyl radical results in formation of a complex containing an iron(II) center coordinated to an iminobenzosemiquinonate radical, that to the best of our knowledge has no synthetic precedence. Further oxidation leads to a complex best described as a ferric center bound to the iminiobenzosemiquinate radical. The electronic structures of these complexes were determined with the aid of spectroscopic and computational methods. Several monoiron(II) complexes were also prepared to model the active-site structure of β-diketone dioxygenase (Dke1). For this purpose, we employed the ^Ph2Tp supporting ligand and acac^X substrate ligands, where acac^X represents the anion of dialkyl malonate. Upon exposure to O₂ in toluene it was found that the complexes exhibited reactivity similar to Dke1, although at a much slower rate than the native enzyme.

Subjects/Keywords: Chemistry; Inorganic

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Bittner, M. M. (2014). Investigations of synthetic models of mononuclear nonheme iron dioxygenases. (Thesis). Marquette University. Retrieved from http://pqdtopen.proquest.com/#viewpdf?dispub=3642714

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Bittner, Michael M. “Investigations of synthetic models of mononuclear nonheme iron dioxygenases.” 2014. Thesis, Marquette University. Accessed February 23, 2020. http://pqdtopen.proquest.com/#viewpdf?dispub=3642714.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Bittner, Michael M. “Investigations of synthetic models of mononuclear nonheme iron dioxygenases.” 2014. Web. 23 Feb 2020.

Vancouver:

Bittner MM. Investigations of synthetic models of mononuclear nonheme iron dioxygenases. [Internet] [Thesis]. Marquette University; 2014. [cited 2020 Feb 23]. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3642714.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Bittner MM. Investigations of synthetic models of mononuclear nonheme iron dioxygenases. [Thesis]. Marquette University; 2014. Available from: http://pqdtopen.proquest.com/#viewpdf?dispub=3642714

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Pennsylvania

30. Wu, Yaoting. Structural Diversity Of Nanocrystal Self-Assembly And Their Unique Optical Properties.

Degree: 2017, University of Pennsylvania

URL: https://repository.upenn.edu/edissertations/2889

► The colloidal nanocrystals (NCs) are nanometer-sized inorganic particles with distinctive properties from their extremely small size, high surface-to-volume ratio, and diverse morphologies. By tuning the… (more)

▼ The colloidal nanocrystals (NCs) are nanometer-sized inorganic particles with distinctive properties from their extremely small size, high surface-to-volume ratio, and diverse morphologies. By tuning the assembly conditions, the NC will form diverse superstructures with specific crystalline lattices and precise chemical compositions. The interparticle coupling and collective physical phenomena that emerge makes these superstructures promising as novel optical and electrical materials. Understanding the driving force of assembly, crystal structure and defects of the superlattice, and their relationship with properties are still incomplete. In this work, we perform cation exchange, asymmetric modification, and oxidative etching to create distinctive NC building blocks for self-assembly. We characterize the diverse crystal structures comprised of these building blocks and investigate the driving factors behind the structure formation. We perform ligand exchange to enhance the coupling of neighboring building blocks and investigate the enhanced carrier transfer in the NC superlattices with the help of ultrafast spectroscopy. In the meantime, In-situ grazing incidence small-angle X-ray scattering (GISAXS) technique allows us to understand the kinetics of ligand exchange in the performed NC superlattice membranes for the first time. The ligand exchange will precisely control the inter-particle spacing and extent of coupling in the NC superlattice. NC superlattices have predominantly been producing as extend 2D thin films. In this work, we explore the use of emulsion confinement and non-solvent destabilization-driven self-assembly technique to prepare discrete 3-D superstructures (superparticles, superballs, etc.) with distinctive morphologies and crystalline structure. Their strong mechanical strength allows multi-step post-treatments including ligand exchange, thermal annealing, which further enhance the atomic fusion and orientational coupling, and generate promising optical and electrical properties.

Subjects/Keywords: Inorganic Chemistry

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Wu, Y. (2017). Structural Diversity Of Nanocrystal Self-Assembly And Their Unique Optical Properties. (Thesis). University of Pennsylvania. Retrieved from https://repository.upenn.edu/edissertations/2889

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Wu, Yaoting. “Structural Diversity Of Nanocrystal Self-Assembly And Their Unique Optical Properties.” 2017. Thesis, University of Pennsylvania. Accessed February 23, 2020. https://repository.upenn.edu/edissertations/2889.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Wu, Yaoting. “Structural Diversity Of Nanocrystal Self-Assembly And Their Unique Optical Properties.” 2017. Web. 23 Feb 2020.

Vancouver:

Wu Y. Structural Diversity Of Nanocrystal Self-Assembly And Their Unique Optical Properties. [Internet] [Thesis]. University of Pennsylvania; 2017. [cited 2020 Feb 23]. Available from: https://repository.upenn.edu/edissertations/2889.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Wu Y. Structural Diversity Of Nanocrystal Self-Assembly And Their Unique Optical Properties. [Thesis]. University of Pennsylvania; 2017. Available from: https://repository.upenn.edu/edissertations/2889

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Open Access Theses and Dissertations