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Articles 1 - 15 of 15
Full-Text Articles in Inorganic Chemistry
Mechanistic Investigation Of C—C Bond Activation Of Phosphaalkynes With Pt(0) Complexes, Roberto M. Escobar, Abdurrahman C. Ateşin, Christian Müller, William D. Jones, Tülay Ateşin
Mechanistic Investigation Of C—C Bond Activation Of Phosphaalkynes With Pt(0) Complexes, Roberto M. Escobar, Abdurrahman C. Ateşin, Christian Müller, William D. Jones, Tülay Ateşin
Research Symposium
Carbon–carbon (C–C) bond activation has gained increased attention as a direct method for the synthesis of pharmaceuticals. Due to the thermodynamic stability and kinetic inaccessibility of the C–C bonds, however, activation of C–C bonds by homogeneous transition-metal catalysts under mild homogeneous conditions is still a challenge. Most of the systems in which the activation occurs either have aromatization or relief of ring strain as the primary driving force. The activation of unstrained C–C bonds of phosphaalkynes does not have this advantage. This study employs Density Functional Theory (DFT) calculations to elucidate Pt(0)-mediated C–CP bond activation mechanisms in phosphaalkynes. Investigating the …
N–((2–Acetylphenyl)Carbamothioyl)Benzamide: Synthesis, Crystal Structure Analysis, And Theoretical Studies, Akin Oztaslar, Hakan Arslan
N–((2–Acetylphenyl)Carbamothioyl)Benzamide: Synthesis, Crystal Structure Analysis, And Theoretical Studies, Akin Oztaslar, Hakan Arslan
Karbala International Journal of Modern Science
N–((2–Acetylphenyl)carbamothioyl)benzamide has been synthesized and characterized. The molecular conformation of the investigated compound is stabilized by C16–H16B⋅⋅⋅O2i (i: 1+x, y, z) intermolecular and C14–H14⋅⋅⋅S1, N2–H2⋅⋅⋅O2, and N2–H2⋅⋅⋅O1 intramolecular H–bonds. All DFT calculations have been implemented at the B3LYP level with the 6–311G(d,p) basis set. The optimized molecular structure parameters have been compared with the experimental one in the solid phase. The energy gap, global chemical reactivity descriptor parameters, MEP, Fukui functions, DoS, NLO, and NBO analysis were also computed and investigated. The intermolecular interactions and their energies are evaluated using Hirshfeld surface and energy framework analyses. To determine …
Water-Soluble Palladium, Copper, And Nickel Catalysts And Their Formation In Ligand-Free Suzuki-Miyaura Cross-Coupling Reactions, Priya Karna
Theses and Dissertations--Chemistry
Transition-metal catalyzed Suzuki-Miyaura (SM) cross coupling is a powerful synthetic method for constructing carbon-carbon and carbon-heteroatom bonds in designing organic compounds, agrochemicals, pharmaceuticals, and precursors for materials. However, the nature of catalysis and identity of the transition metal catalysts used in these reactions remain under debate or unknown. This dissertation reports the studies of three metals: Pd, Cu, and Ni. Pd-nanocluster catalysts and their formation in ligand-free SM reactions with Pd(II) nitrate as a precatalyst was investigated. The catalysts are water-soluble neutral Pd tetramer and trimer in their singlet electronic states as identified by UV-Vis absorption spectroscopy and are formed …
Computational Comparison Of Platinum, Base Metals, And Binary Intermetallic Compounds’ Efficiency In Hydrogenation Catalysis, Lauren M. Sayler
Computational Comparison Of Platinum, Base Metals, And Binary Intermetallic Compounds’ Efficiency In Hydrogenation Catalysis, Lauren M. Sayler
MSU Graduate Theses
In the petroleum industry, platinum is used as a catalyst in hydrogenation reactions during petroleum refining. Although platinum is extremely effective as a catalyst, it is expensive. This is an investigation into platinum and what characteristics make it so efficient, with the end goal of finding intermetallic compounds composed of base metals that are as effective in hydrogenation catalysis. The metals used in this investigation are Fe, Co, Ni, Mo, and W. The research performed here is computational and used to support and direct decisions made in the laboratory. The computation is first-principle, which is accomplished using Vienna Ab initio …
Computational Investigation Of The Ionization Potential Of Lead Sulfide Quantum Dots, Jessica Beyer
Computational Investigation Of The Ionization Potential Of Lead Sulfide Quantum Dots, Jessica Beyer
Scripps Senior Theses
The purpose of this work was to determine the impact of quantum dot size on ionization potential and to determine how the presence of carbonyl-based ligands affect the ionization potential of lead sulfide quantum dot systems. Ionization potential (IP) is defined as the energy required to remove an electron from an atom, molecule, or material. IP helps scientists determine how reactive the material of interest is, which is crucial information when manufacturing nanomaterials. Accurate quantum chemical calculations of ionization potential are challenging due to the computational cost associated with the numerical solution of the Dyson equation. In this work, the …
Multiscale Molecular Modeling Studies Of The Dynamics And Catalytic Mechanisms Of Iron(Ii)- And Zinc(Ii)-Dependent Metalloenzymes, Sodiq O. Waheed
Multiscale Molecular Modeling Studies Of The Dynamics And Catalytic Mechanisms Of Iron(Ii)- And Zinc(Ii)-Dependent Metalloenzymes, Sodiq O. Waheed
Dissertations, Master's Theses and Master's Reports
Enzymes are biological systems that aid in specific biochemical reactions. They lower the reaction barrier, thus speeding up the reaction rate. A detailed knowledge of enzymes will not be achievable without computational modeling as it offers insight into atomistic details and catalytic species, which are crucial to designing enzyme-specific inhibitors and impossible to gain experimentally. This dissertation employs advanced multiscale computational approaches to study the dynamics and reaction mechanisms of non-heme Fe(II) and 2-oxoglutarate (2OG) dependent oxygenases, including AlkB, AlkBH2, TET2, and KDM4E, involved in DNA and histone demethylation. It also focuses on Zn(II) dependent matrix metalloproteinase-1 (MMP-1), which helps …
The Design And Characterization Of Gold Nanoclusters As Elementary Building Blocks, Heather Gaebler
The Design And Characterization Of Gold Nanoclusters As Elementary Building Blocks, Heather Gaebler
Theses and Dissertations (Comprehensive)
Gold nanoclusters with diameters in the quantum size regime (< ~2 nm) are promising building blocks for the design of novel nanomaterials as they exhibit unique size-dependent properties that can be altered and fine-tuned. The research outlined in this PhD thesis employs density functional theory to construct and analyze small ligand-protected cage and rod-shaped nanoclusters. Chapter 2 reports stable halide-protected gold nanocages that were engineered to have a closed-shell valence electron count of 18. This study finds that nanocages comprised of 19 and 20 gold atoms can be converted into stable magic number species containing 18 valence electrons by modifying their charged states via adsorption of halide ligands to the cage’s surface. Chapter 3 reports stable ligand-protected gold nanoclusters with a tetrahedral Au4 core that were engineered to have a closed-shell valence electron count of 2. This study investigates the structural and electronic effects of halide and alkoxy ligands on the tetrahedral nanocluster and concludes that the results support the broader conclusion that it’s possible to fine-tune the stability and electronic properties of small gold nanoclusters using appropriate ligands. Chapter 4 reports stable gold nanorods that have diameters in the quantum regime that were constructed from elementary building blocks that contain “halide-staples”. This study presents different orientations of the “halide-staple” motifs on …
Gold (I) Tetrathiomolybdate Clusters: Synthesis, Characterization, Computational Studies, And Reactivity With Thiophenol And Selenophenol, Dhirgam Humaidy
Gold (I) Tetrathiomolybdate Clusters: Synthesis, Characterization, Computational Studies, And Reactivity With Thiophenol And Selenophenol, Dhirgam Humaidy
Electronic Theses and Dissertations
This thesis describes the synthesis and reactivity of heterometallic complexes containing medicinally active Au(I) and tetrathiomolybdate, [MoS4]2-. The research is motivated by the idea of multifunctional drugs, which are designed to treat diseases through two or more mechanisms of action. Five clusters of the general form, [MoS4(AuL)2] were prepared: C-1 (L=IPr), C-2 (L=IBzMe), C-3 (L=IMes), C-4 (L=PPh3), and C-5 (L=PEt3). The clusters with NHC ligands, C-1, C-2, and C-3 were prepared for the first time and thoroughly characterized by 1H NMR,13C{1H} …
Transition Metal Computational Catalysis: Mechanistic Approaches And Development Of Novel Performance Metrics, Brett Anthony Smith
Transition Metal Computational Catalysis: Mechanistic Approaches And Development Of Novel Performance Metrics, Brett Anthony Smith
Doctoral Dissertations
Computational catalysis is an ever-growing field, thanks in part to the incredible progression of computational power and the efficiency offered by our current methodologies. Additionally, the accuracy of computation and the emergence of new methods that can decompose energetics and sterics into quantitative descriptors has allowed for researchers to begin to identify important structure-function relationships that predict the properties of unexplored subspaces within the overall chemical space. Catalytic descriptors have been used frequently in data driven high-throughput computational screenings. With the use of machine learning, a large portion of the chemical space an be predicted in matter of minutes or …
Computational And Experimental Investigations Of Alkali Cation Interactions At The Rutile – Water Interface, Isaac Johnston
Computational And Experimental Investigations Of Alkali Cation Interactions At The Rutile – Water Interface, Isaac Johnston
All Dissertations
Overall, the objective of this dissertation was to investigate the degree of sorption for the alkali cations on rutile to ascertain the impact of different cation properties, such as ion size and charge density, on sorption mechanics as well as probe how the ion may alter the surface – aqueous interface. Initial molecular dynamic simulations and batch experiments showed minimal surface sorption for any alkali cation at relatively low concentrations while simultaneously suggesting the enthalpy of deprotonation shifts slightly in the presence of the alkali cations at different ionic strengths. The cations are likely causing small reorientations of the near-surface …
Turning Ligands On Their Side: Computational Investigation Into The Binding Of N2o And N2 In Transition Metal Complexes, Cole Donald
Electronic Theses and Dissertations
Common greenhouse gas nitrous oxide (N2O) is a thermodynamically potent and environmentally benign oxidant, making it a desirable target for metal center activation. Unfortunately, N2O is a poor ligand for transition metals due to its weak sigma-donating and pi-accepting properties; as a result, few transition metal complexes capable of interacting with N2O have been found. As the primary source of all nitrogen in organisms, abundant gas dinitrogen (N2) is a crucially important tiny molecule and an essential part of daily existence. However, due to its inertness, it has limited practical uses in …
Exploring Structure-Function Relationship In Small-Molecular Catalysts Using Computational And Experimental Methodologies, Avik Bhattacharjee
Exploring Structure-Function Relationship In Small-Molecular Catalysts Using Computational And Experimental Methodologies, Avik Bhattacharjee
Dissertations and Theses
Molecular modeling is a useful tool in the field of catalyst design for various processes. The use of Density Functional Theory (DFT) is routine in almost every discipline of chemistry. This allows for a deeper understanding of a molecular system even in situations where implementation of an experimental technique is unfeasible. However, without the right choice of theory and insufficient description, the model becomes susceptible to produce ambiguous results. This often leads to poor correlation with experimental findings hence an incomplete understanding of the system under study. Hence, to acquire a thorough knowledge of the intricacies involved in a system, …
Calcium Bistriflimide-Mediated Sulfur (Vi)–Fluoride Exchange (Sufex): Mechanistic Insights Toward Instigating Catalysis, Nicholas Ball, Brian Han, Samuel R. Khasnavis, Matthew Nwerem, Michael Bertagna, O Maduka Ogba
Calcium Bistriflimide-Mediated Sulfur (Vi)–Fluoride Exchange (Sufex): Mechanistic Insights Toward Instigating Catalysis, Nicholas Ball, Brian Han, Samuel R. Khasnavis, Matthew Nwerem, Michael Bertagna, O Maduka Ogba
Pomona Faculty Publications and Research
We report a mechanistic investigation of calcium bistriflimide-mediated sulfur(VI)–fluoride exchange (SuFEx) between sulfonyl fluorides and amines. We determine the likely pre-activation resting state─a calcium bistriflimide complex with ligated amines─thus allowing for corroborated calculation of the SuFEx activation barrier at ∼21 kcal/mol, compared to 21.5 ± 0.14 kcal/mol derived via kinetics experiments. Transition state analysis revealed: (1) a two-point calcium-substrate contact that activates the sulfur(VI) center and stabilizes the leaving fluoride and (2) a 1,4-diazabicyclo[2.2.2]octane additive that provides Brønsted-base activation of the nucleophilic amine. Stable Ca–F complexes upon sulfonamide formation are likely contributors to inhibited catalytic turnover, and a proof-of-principle redesign …
Understanding Interfacial Reactions Initiating On Electrode Materials For Energy Storage Technologies, Jingnan Li
Understanding Interfacial Reactions Initiating On Electrode Materials For Energy Storage Technologies, Jingnan Li
Graduate Theses and Dissertations
Since the first generation of lithium-ion batteries featured lithium cobalt oxide cathode and carbon anode commercialized in the 1990s, the high-capacity materials with lower cost are in demand to further increase the battery energy density. Lithium metal and silicon anode are promising high-capacity anode materials to achieve next-generation lithium batteries. However, both the materials actively react in electrolytes and suffer from dramatic volume change. Therefore, a reliable passivation layer at the electrolyte/electrode interphase (i.e., solid electrolyte interphase, or “SEI”) is required to support the long-term cycling of both materials. Cetrimonium hydro fluoride (CTAHF2) has been proposed and synthesized as an …
Multilevel Computational Investigation Into The Dynamics And Reaction Mechanisms Of Non-Heme Iron And 2-Oxoglutarate Dependent Enzymes, Shobhit Sanjeev Chaturvedi
Multilevel Computational Investigation Into The Dynamics And Reaction Mechanisms Of Non-Heme Iron And 2-Oxoglutarate Dependent Enzymes, Shobhit Sanjeev Chaturvedi
Dissertations, Master's Theses and Master's Reports
Computational chemistry methods have been extensively applied to investigate biological systems. This dissertation utilizes a multilevel computational approach to explore the dynamics and reaction mechanisms of two groups of enzymes belonging to non-heme Fe(II) and 2-oxoglutarate (2OG) dependent superfamily – histone lysine demethylases from class 7 and ethylene forming enzyme (EFE). Chapter 2 uncovers the role of conformational dynamics in the substrate selectivity of histone lysine demethylases 7A and 7B. The molecular dynamics (MD) simulations of the two enzymes revealed the importance of linker flexibility and dynamics in relative orientations of the reader (PHD) and the catalytic (JmjC) domains. Chapter …