Download or read book The Synthesis Characterization and Oxidation state Dependent Reactivity of Rh I Complexes Formed from Novel Redox active Ligands written by Caroline Cassano Slone and published by . This book was released on 1997 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Synthesis Characterization and Reactivity Studies of Iron Complexes Supported by the Redox active ONO Ligand written by Janice Lin Wong and published by . This book was released on 2014 with total page 123 pages. Available in PDF, EPUB and Kindle. Book excerpt: The work reported herein primarily focuses on the development of new platforms for multi-electron reactivity using iron complexes supported by a redox-active pincer-type ligand. This dissertation details the synthesis, characterization, and reactivity of iron complexes coordinated to the redox-active [ONO] ([ONO]H3 = bis(3,5-di-[tert]-butyl-2-phenol)amine) ligand. Chapter 1 provides a general background on ligand-centered and metal-centered redox reactivity. Specifically, the characteristics of redox-active ligands and their ability to promote multi-electron reactivity at redox-inert metal centers is presented. In addition, iron-catalyzed organic transformations in which the metal center undergoes redox changes is also discussed. Finally, ligand-enabled redox reactions mediated by iron complexes containing redox-active ligands is described. Chapter 2 reports on the complexation of bis(3,5-di-[tert]-butyl-2-phenoxy)amine, [ONHO], and the redox-active [ONO] ligands by iron centers to afford a new family of iron complexes. Characterizations of each compound through a battery of analytical techniques reveal the oxidation states of the metal center and ligand. Furthermore, the electronic properties of each complex were investigated in order to evaluate their potential to facilitate multi-electron reactivity. Chapter 3 details the reactivity of the [ONO]Fe platform. Metathesis reactions are conducted with [ONO [superscript q] Fe [superscript III] X2 (X = Cl, N[SiMe3]2 complexes, demonstrating the capability of the fully-oxidized [ONO [superscript q]−1 to act as a two-electron acceptor to generate the fully reduced [ONO [superscript cat]3− that is coordinated to an iron(III) center. Similarly, oxidation of [ONO[superscript cat] Fe [superscript III] (py)3 (py = pyridine) using dihalogens result in two-electron oxidations of the tridentate ligand while the metal oxidation state remains the same. These redox reactions showcase the ability of the [ONO] ligand platform to undergo reversible two-electron oxidation state changes, allowing multi-electron reactivity to occur at the iron center. The synthesis and characterization of two novel bimetallic complexes of the form [ONO]M'[ONO]2 M (M' = Fe, Zn; M = Fe) are presented in Chapter 4. The rich redox profiles of both complexes suggest that they can potentially impart unique cooperative bimetallic reactivity. The synthetic techniques developed to prepare these complexes lay the foundation for a general method to access new bimetallic combinations that could be promising for multi-electron reactivity. Finally, Chapter 5 discusses the synthesis, characterization, and electronic comparisons between two homoleptic tris-iminosemiquinonate chromium(III) compounds. While one is coordinated to three N,N'-bis(3,5-dimethylphenyl)acenapthenediimino-semiquinonate, (dmp-ADI [superscript sq])1−, ligands, the other contains three N,N'-bis(3,5-dimethylphenyl)phenanthrenediimino-semiquinonate, (dmp-PDIsq)1− ligands. The differences in the electronic properties between each complex likely stems from variation in the diimine ligand backbones. However, further investigation is required to completely understand the complicated behaviors of such complexes, both of which apparently exhibit intramolecular anti-ferromagnetic properties.
Download or read book Dissertation Abstracts International written by and published by . This book was released on 2005 with total page 860 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book American Doctoral Dissertations written by and published by . This book was released on 1997 with total page 806 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book The Synthesis Characterization and Reactivity of High Oxidation State Rhenium Imido and Oxo Complexes written by Tiow-Gan Ong and published by . This book was released on 2000 with total page 466 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Experimental and Theoretical Approaches to Actinide Chemistry written by John K. Gibson and published by John Wiley & Sons. This book was released on 2018-03-19 with total page 534 pages. Available in PDF, EPUB and Kindle. Book excerpt: A review of contemporary actinide research that focuses on new advances in experiment and theory, and the interplay between these two realms Experimental and Theoretical Approaches to Actinide Chemistry offers a comprehensive review of the key aspects of actinide research. Written by noted experts in the field, the text includes information on new advances in experiment and theory and reveals the interplay between these two realms. The authors offer a multidisciplinary and multimodal approach to the nature of actinide chemistry, and explore the interplay between multiple experiments and theory, as well as between basic and applied actinide chemistry. The text covers the basic science used in contemporary studies of the actinide systems, from basic synthesis to state-of-the-art spectroscopic and computational techniques. The authors provide contemporary overviews of each topic area presented and describe the current and anticipated experimental approaches for the field, as well as the current and future computational chemistry and materials techniques. In addition, the authors explore the combination of experiment and theory. This important resource: Provides an essential resource the reviews the key aspects of contemporary actinide research Includes information on new advances in experiment and theory, and the interplay between the two Covers the basic science used in contemporary studies of the actinide systems, from basic synthesis to state-of-the-art spectroscopic and computational techniques Focuses on the interplay between multiple experiments and theory, as well as between basic and applied actinide chemistry Written for academics, students, professionals and researchers, this vital text contains a thorough review of the key aspects of actinide research and explores the most recent advances in experiment and theory.
Download or read book Synthesis Reactivity and Computational Studies of Redoxactive Indium Thiolate Complexes written by Padmapriya Srinivasan and published by . This book was released on 2022 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Green Chemistry initiatives have recently been at the forefront of both industrial and academic communities in order to address fundamental scientific challenges of protecting human health and the environment. The Twelve Principles of Green Chemistry, of which catalysis is a primary tenet and the main motivation for this project, has led the path to reduce waste production in the chemical industry. The principle of catalysis states that catalytic reactions necessarily produce less waste than stoichiometric reactions. Traditionally, precious and toxic heavy transition metals such as platinum and palladium have been used as metal centres in catalysts because of their stability, favourable redox properties, and ease of characterization. These concerns prompted this research in finding more environmentally friendly alternatives as metal centres in catalysis, such as main group complexes. Indium is a heavy main group metal that is environmentally benign. It is most stable in the +3 oxidation state and, notably, does not possess other readily accessible oxidation states. To make indium complexes redox-active, so-called "non-innocent" redox-active ligands are being explored. The current work seeks to synthesize a series of redox-active indium catalysts with varied steric bulk about the indium centre and different redox-active ligands. The goals of this study are to first synthesize and structurally characterize organometallic indium compounds with the redox-active ligand 2-amninobenzenethiol, and then test the reactivity of indium complexes with dithiolate ligands using mild oxidizing agents. A third goal is to use DFT methods to rationalize the synthesized complexes in terms of structure, reactivity, bonding motifs, and in interpreting the experimental spectroscopic data.
Download or read book Synthesis Characterization and Reactivity of Some Mixed metal Rh and Au Complexes Containing Primarily Phophine and Phosphite as Ligands written by Angela Marie Buehler and published by . This book was released on 1985 with total page 158 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Book of Abstracts written by and published by . This book was released on 2000 with total page 776 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Olefin Polymerization written by Walter Kaminsky and published by Wiley-VCH. This book was released on 2006-08-18 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: With an enormous velocity, olefin polymerization has expanded to one of the most significant fields in polymers since the first industrial use about 50 years ago. In 2005, 100 million tons of polyolefins were produced - the biggest part was catalyzed by metallorganic compounds. The Hamburg Macromolecular Symposium 2005 with the title "Olefin Polymerization" involved topics such as new catalysts and cocatalysts, kinetics, mechanism and polymer reaction engineering, synthesis of special polymers, and characterization of polyolefins. The conference combined scientists from different disciplines to discuss latest research results of polymers and to offer each other the possibility of cooperation. This is reflected in this volume, which contains invited lectures and selected posters presented at the symposium.
Download or read book Spin States in Biochemistry and Inorganic Chemistry written by Marcel Swart and published by John Wiley & Sons. This book was released on 2015-09-17 with total page 472 pages. Available in PDF, EPUB and Kindle. Book excerpt: It has long been recognized that metal spin states play a central role in the reactivity of important biomolecules, in industrial catalysis and in spin crossover compounds. As the fields of inorganic chemistry and catalysis move towards the use of cheap, non-toxic first row transition metals, it is essential to understand the important role of spin states in influencing molecular structure, bonding and reactivity. Spin States in Biochemistry and Inorganic Chemistry provides a complete picture on the importance of spin states for reactivity in biochemistry and inorganic chemistry, presenting both theoretical and experimental perspectives. The successes and pitfalls of theoretical methods such as DFT, ligand-field theory and coupled cluster theory are discussed, and these methods are applied in studies throughout the book. Important spectroscopic techniques to determine spin states in transition metal complexes and proteins are explained, and the use of NMR for the analysis of spin densities is described. Topics covered include: DFT and ab initio wavefunction approaches to spin states Experimental techniques for determining spin states Molecular discovery in spin crossover Multiple spin state scenarios in organometallic reactivity and gas phase reactions Transition-metal complexes involving redox non-innocent ligands Polynuclear iron sulfur clusters Molecular magnetism NMR analysis of spin densities This book is a valuable reference for researchers working in bioinorganic and inorganic chemistry, computational chemistry, organometallic chemistry, catalysis, spin-crossover materials, materials science, biophysics and pharmaceutical chemistry.
Download or read book Synthesis Reactivity and Multi electron Redox Behavior of a Bis phenoxy amide Ligand Coordinated to a Tantalum Metal Center written by Ryan A. Zarkesh and published by . This book was released on 2012 with total page 150 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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 ligand to store multiple electron equivalents for oxidative addition and reductive elimination reactions. Chapter 1 provides an introduction to the characteristics of redox-active ligands and provides an overview of group transfer reactions involving redox-active ligands. The previous published results of bidentate redox-active ligands coordinated to Group IV d0 metals are discussed in terms of their decomposition side reactions. Chapter 2 describes the coordination of a known tridentate redox-active bis(phenoxy)amide ligand, (ONO), to a d0 tantalum(V) metal center and the examination of the redox properties of the resulting chloro oxidation products by electrochemical and spectroscopic methods. Chapter 3 examines the reactivity of the (ONO)TaR2 complexes in the general context of organometallic chemistry with a focus on protonolysis and reactivity with aryl azides, a known source of nitrene fragments upon oxidation. Chapter 4 examines the reactivity of the (ONO)TaX2 (X = Me, Cl) compounds with bulky diazoalkanes, a known carbene transfer reagent. The (ONO)TaCl2 complex proved to be a competent catalyst to generate cyclopropanes from styrene and the corresponding diazoalkane. Chapter 5 explores the utilization of the (ONO) ligand to store electron equivalents for the catalytic nitrene-nitrene coupling reactions with organoazides to afford organodiazenes. Finally, Chapter 6 addresses the electronic considerations of a related redox-active triamido ligand in an effort to tune the ligand's redox potentials.
Download or read book Synthesis Characterization and Reactivity of Iron Complexes with N donor Ligands in Relation to Oxygenation of Hydrocarbons written by Remle Çelenligil-Çetin and published by . This book was released on 2004 with total page 766 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Synthesis Characterization and Reactivity of Ru II and Rh I Hydrocarbyl and Hydride Complexes written by John P. Lee and published by . This book was released on 2008 with total page 274 pages. Available in PDF, EPUB and Kindle. Book excerpt: Keywords: hydride complexes, hydrocarbyl complexes, rhodium, ruthenium.
Download or read book Journal of the American Chemical Society written by American Chemical Society and published by . This book was released on 1975 with total page 1062 pages. Available in PDF, EPUB and Kindle. Book excerpt: Proceedings of the Society are included in v. 1-59, 1879-1937.
Download or read book Inter and Intramolecular Aryl Nitroso Copper Mediated Redox Reactions written by Farshid Effaty and published by . This book was released on 2021 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: The redox conversions of hydroxylamine (NH2OH) are biologically relevant because this molecule serves as a nitric oxide donor in mammals under certain conditions. The analogous arylhydroxylamine compounds (ArNHOH, where Ar is an aryl group) display similar chemistry, with the advantage of fewer side-reactions. Thus, there has recently been increased interest into investigations of the reactivity of arylhydroxylamines with metal complexes as mimics of the biologically relevant reactions of NH2OH with copper or iron. Oxidation of arylhydroxylamines yields nitrosoarenes (ArNO), which are structurally and electronically versatile redox-active molecules. Their corresponding metal complexes are stable mimics of O2 and HNO complexes transiently found in nature and catalytic cycles. This stability allows for a systematic survey of the structure and redox state of ArNO metal complexes. The metal-mediated transformations between ArNHOH, ArNO and other relevant nitrogen-based groups, however, are not well understood. Herein, in two different reports, we address the reactivity of ArNHOH and ArNO groups with copper complexes. In the first study, a series of complexes is prepared by self-assembly of copper(I) precursors and arylnitroso species. The nature of the copper(I) supporting ligand (bi-, tri- or tetradentate, as well as secondary vs. tertiary amine donors) and the electronic nature of the arylnitroso species (electron-donating or withdrawing substituents) are varied. The stoichiometry of the reaction, the topology, and the electronic properties of the adducts are characterized by UV-Vis spectroscopy, single crystal X-ray diffraction, and DFT methods. The more electron-rich ligands and the more electron-poor arylnitroso species lead to an inner-sphere electron transfer and formation of copper(II)-(arylnitrosyl radical) complexes bearing a linkage topology that depends on the denticity of the supporting ligand. These results provide a canvas by which to predict the products of similar self-assembled redox reactions. In the second study, the synthesis of an unprecedented copper(I)-arylhydroxylamine complex is reported. The reactivity of the arylhydroxylamine is arrested by the presence of an intramolecular hydrogen bond that stabilizes the weakly bound hydroxylamine. Upon two-electron oxidation, a copper(II)-(arylnitrosyl radical) complex is formed, which crystallizes as a copper(I) species with an uncoordinated arylnitroso function. This validates that such ligands may enable ligand redox chemistry and hemilability in copper complexes. Such tethered arylnitroso complexes present new opportunities for two-electron chemistry in earth-abundant metal catalysis. In a nutshell, this thesis highlights unique electron-transfer events and redox conversions about the N-O bond in copper complexes. The main finding is the characterization of an intermediate redox state in-between ArNHOH and ArNO, namely the arylnitrosyl radical anion, ArNO-, which is stable only when coordinated.
Download or read book Organic Redox Chemistry written by Jun-Ichi Yoshida and published by John Wiley & Sons. This book was released on 2022-03-07 with total page 260 pages. Available in PDF, EPUB and Kindle. Book excerpt: Organic Redox Chemistry Explore the most recent advancements and synthesis applications in redox chemistry Redox chemistry has emerged as a crucial research topic in synthetic method development. In Organic Redox Chemistry: Chemical, Photochemical and Electrochemical Syntheses, some key researchers in this field, including editors Dr. Frédéric W. Patureau and the late Dr. Jun-Ichi Yoshida, deliver an insightful exploration of this rapidly developing topic. This book highlights electron transfer processes in synthesis by using different techniques to initiate them, allowing for a multi-directional perspective in organic redox chemistry. Covering a wide array of the important and recent developments in the field, Organic Redox Chemistry will earn a place in the libraries of chemists seeking a one-stop resource that compares chemical, photochemical, and electrochemical methods in organic synthesis.
