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Showing 1 to 20 of 38 for “"High Valent"”.
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High valent element fluorosulfates and fluoride- fluorosulfates
The synthesis of the binary tetrakis(fluorosulfates) of the group 4 elements (Ti, Zr or Hf), all potential Lewis acids in fluorosulfuric acid (HSO3F), was carried out in order to extend the presently known conjugate superacid systems of the type HSO3F-M(SO3F)n. Metal oxidation by …
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Organometallic chemistry of triazacyclononanes and high-valent nickel complexes
Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2026-05-01
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Organometallic chemistry of high-valent palladium and rhodium complexes
Author requested closed access (OA after 2yrs) in Vireo ETD system
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Ligand Manipulation and Reactivity Studies of Organometallic High Valent Palladium Complexes
<p>Catalysis involving high-valent Pd(III) and Pd(IV) complexes has recently shown important applications in the development of new chemical transformations that compliments conventional Pd<super>0/II</super> catalysis.</p><p>However, the Pd(III) or Pd(IV) intermediates cannot be …
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Controlling electronics for the formation of high valent uranium imido complexes
… ligands to assist in the stabilization of low-valent uranium analogues, capable of performing multi-electron chemistry at a single uranium center. Of particular interest to our group are high-valent imido complexes, which are ubiquitous in organometallic and coordination chemistry due to their …
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Oxidative reactivity of high-valent palladium complexes supported by 1,4,7-triisopropyl-1,4,7-triazacyclononane
Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2026-08-01
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Development of systems for isolation of high-valent nickel complexes and their reactivity
… (tacn) ligands for the isolation and study of high-valent nickel and palladium compounds, chiral variants of these ligands were synthesized in attempts to isolate high-valent organometallic nickel complexes that could play a role in enantioselective crosscoupling reactions. Utilizing readily …
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Palladium-mediated C–H Functionalization of Aliphatic Amines via High Valent Palladium(IV) Intermediates
… to oxidize amine-derived palladacycles to high valent PdIV intermediates capable of undergoing a variety of reductive elimination pathways to afford a diverse range of functionalized products. Hypervalent iodine(III) reagents were initially investigated as oxidants in the development of a …
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High Valent Palladium Complexes and Their Role in C-C and C-X Bond Formation Chemistry.
… transfer steps. This translates into a very high barrier of activation since multi-electron processes are kinetically challenging. On the other hand, multi-nuclear complexes are receiving an appreciable interest due to their potential synergetic effect between the metals. To this purpose, …
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Ligand field considerations for the reactivity of high valent metal-oxo complexes and of bimetallic HX splitting photocatalysts
… of low coordinate tris(alkoxide) complexes of divalent and trivalent metals were synthesized and characterized as single metal site models of oxidic metal clusters. Via oxygen atom transfer reactions, d⁰, d¹, and d² early transition metal-oxo complexes were stabilized. Analysis of structural …
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O-O bond formation and the transition metal chemistry of [beta]-diketiminate, siloxide, and triamide ligands
… and examines ligand platforms that can stabilize high valent metal oxo intermediates. Siloxide ligands were used to generate a series of 4-coordinate Cr, Mn, Fe, and Co complexes, but these could not support the corresponding high valent oxo species. Instead, a remarkably stable 4-coordinate Crv …
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Development of base metal-catalyzed C—H functionalization reactions
… center that reacts with oxygen and water to form high-valent iron-oxo intermediates. These species can directly and selectively convert C—H bonds into C—O bonds, even in complex molecule settings. However, the analogous transformation of C—H bonds to C—N and C—C bonds via metallonitrenes and …
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Electronic structure of transition metal ions and clusters
… of the thesis (Chapters 2 and 3) is devoted to high-valent metal-oxo species, both mono- and bimetallic, while Chapter 4 describes some aspects of copper-catalysed carbon-carbon bond formation. Finally, Chapter 5 highlights the role of DFT in computing magnetic and spectroscopic properties of …
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Synthesis, Kinetic and Photocatalytic Studies of Porphyrin-Ruthenium-Oxo Complexes
… of oxidation reactions with wellcharacterized high-valent ruthenium-oxo porphyrin complexes. <br> The <i>trans</i>-dioxoruthenium(VI) porphyrins have been among the best characterized metal-oxo intermediates and their involvement as the active oxidant in the hydrocarbon oxidation have been …
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Bioinspired Mo/W-Oxo Complexes: Synthesis and Reactivity Across Multiple Ligand Scaffolds
… an important model for understanding how high-valent metal-oxo centers and sulfur- rich ligand environments work together to control structure and reactivity. Molybdenum and tungsten complexes were investigated as bioinspired models of these active sites, with particular focus on ligand …
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Mono- and Dinuclear Nonheme Iron Model Complexes: O-O Bond Activation, Structural Characterization and Reactivity Study
… to form the high-valent [(FeIV2(μ-O)(OH)(O)L2]3+ (3A) and [(FeIV2(μ-O)2L2]4+ (4A) was studied. H2O2 and H2O competed for binding to the Fe centers of 1A and 2A, and [H2O2] was rate limiting under the concentrations studied. The presence of base increased the …
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HYPERVALENT IODINE METHODS FOR CARBON–NITROGEN AND CARBON–CARBON BOND FORMATION
… practical and sustainable fashion by using hypervalent iodine reagents. In this dissertation we demonstrate the synthetic applications of λ3-iodane reagents towards the formation of challenging carbon-carbon and carbon-nitrogen bonds in a complementary way to the methods already reported. Chapter …
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Kinetic Studies of the Sulfoxidation of Aryl Methyl Sulfides by Trans-Dioxoruthenium(VI) Porphyrin Complexes
… based on the electrophilic nature of high-valent metal-oxo species. Steric effect of the substituents on the complexes also affected the reactivity order. The kinetic results revealed that the sulfoxidation reaction with these well-characterized dioxoruthenium(VI) complexes is 3 – 4 …
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Alkyl-heteroatom Bond Forming Reactions from the Late Transition Metals
C(sp3)-N bond formation is a potential high value reaction in transition metal catalysis, however, only a handful of examples of this fundamental coupling reaction step have been reported. Presented in this thesis are new efforts to promote this challenging reaction. Group 9 and 10 metals bound by …
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Nondirected C(sp2)–H Activation of (Hetero-)Arenes Through Ligand-Enabled Palladium Catalysis
… class, which has the potential to stabilize high-valent Pd-species and thereby enable challenging transformations. A large variety of ligands were synthesized and evaluated through deuteration studies. The most active of these tridentate ligands showed higher catalytic activity than …
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