Synthesis, Characterization, and Reactivity of First Row Dipyridylazaallyl Transition Metal Complexes PDF Download
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Author: Brenda Frazier
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Category :
Languages : en
Pages : 0
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Author: Brenda Frazier
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Category :
Languages : en
Pages : 0
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Author: Sadie E. Knight
Publisher:
ISBN:
Category : Ligand binding (Biochemistry)
Languages : en
Pages : 276
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Author: Michael Isaac Lipschutz
Publisher:
ISBN:
Category :
Languages : en
Pages : 139
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Recently, the development of more sustainable catalytic systems based on abundant first-row metals, especially nickel, for organic transformations has attracted significant interest. This thesis describes the development of new synthetic methods for the preparation of two-coordinate complexes of a variety of first row transition metals. The physical and spectroscopic properties of these complexes are discussed and the reactivity and catalytic applications of these compounds are also explored. Species of this type are found to catalyze a variety of useful organic transformations using inexpensive metals and ligands.
Author: Thomas R. Porter
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Category :
Languages : en
Pages : 179
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Reactions involving transition metals and organic free radicals are critically important in a variety of chemical and biological processes. Because of their prevalence, there is a fundamental interest in better understanding these types of reactions to fully realize their potential for new applications. The work presented in this dissertation describes the free radical reactivity and thermochemistry of several different transition metal systems with stable organic radicals. Chapter 1 provides an introduction to transition metal reactivity involving organic free radicals. Chapter 2 describes the catalytic disproportionation of a hydroxylamine by (TMP)Fe[superscript III]-OH (TMP = meso-tetramesityl porphyrin) and some of the radical reactions that make up the catalytic cycle. Chapter 3 describes the preparation, structural characterization and thermochemistry of a previously unreported stable organic radical, [superscript t]Bu2NPArO* (2,6-di-tert-butyl-4-(4'-nitrophenyl)phenoxyl). Chapter 4 describes the preparation of several [Tp[superscript tBu]Cu[superscript II]]+ (Tp[superscript tBu] = hydro-tris(3-tert-butyl-pyrazolyl)borate) and [Tp[superscript tBuMe]Cu[superscript II]]+ (Tp[superscript tBu]Me = hydro-tris(3-tert-butyl-5-methyl-pyrazolyl)borate) alkoxide compelxes as models for potential intermediates in copper/radical alcohol oxidation catalysis. Treating these complexes with stable radicals such a [superscript t]Bu3ArO* (2,4,6-tri-tert-butyl-phenoxyl) did not result in alkoxide oxidation despite having a large driving force. From these studies, we conclude driving force is not a primary predictor for copper/radical alcohol oxidation. Chapter 5 discusses the coordination chemistry of [Tp[supercscript tBu]Cu[superscript II]]+ and [Tp[superscript tBu]Zn[superscript II]]+ with 4-nitro-phenols. With the bulky 2,6-disubstituted 2,6-di-tert-butyl-4-nitro-phenoxide, coordination to either metal occurs through a nitronate resonance form. The 2,6-unsubstituted 4-nitro-phenol binds through the phenoxide resonance form. Chapter 6 highlights the large kinetic barrier for ketone reduction or oxidation by titanocene(III/IV) and the hydrogen atom donor/acceptor, [superscript t]Bu3ArO(-H). Finally, Chapter 7 describes the selective and stoichiometric reduction of aromatic and aliphatic nitro groups by photoreduced titanium dioxide nanoparticles in acidic aqueous solutions. From thermochemical analysis, it is likely that these reactions proceed through a rate determining H+/e- transfer.
Author: John C. Linehan
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Category :
Languages : en
Pages : 514
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Author: David Morris Hamilton
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Category :
Languages : en
Pages : 206
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Author: John Richard Severn
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Category :
Languages : en
Pages :
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Author: Priyabrata Ghana
Publisher: Springer
ISBN: 9783030026240
Category : Science
Languages : en
Pages : 345
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This book explores the development of the first open-shell heavier tetrylidyne complexes featuring a tetrel-centered unpaired electron, and unprecedented metallatetrylidynes containing a multiply-bonded, linear-coordinated single heavier tetrel atom embedded between two metal centers. The chemistry of compounds featuring triple bonds of the heavier Group-14 elements Si–Pb with transition metals is a very challenging research area, which combines modern molecular main-group element with transition-metal chemistry, and is of fundamental importance for the understanding of chemical bonding. During the last 15 years, the research in this area has witnessed considerable progress in isolating a series of closed-shell tetrylidyne complexes. However, despite numerous attempts, open-shell tetrylidyne complexes and heavier group 14 element congeners of metallacarbynes and carbide complexes remained inaccessible. In this book, readers will find more about the reactivity studies of these novel complexes that uncovered a plethora of exceptional products, including a novel m3-silicido complex, the first dimetallasilacumulene with a linear, two-coordinated single silicon atom and the first compounds of planar tetracoordinated silicon (ptSi) (Anti-van’t Hoff-Le Bell Silicon). Readers will also learn about the isolation and full characterization of the first room-temperature stable disilavinylidene, a silicon analogue of the very reactive vinylidenes (R2C=C:), and the first intermetallic plumbylidyne ligand transfer reactions.
Author: Lothar Stahl
Publisher:
ISBN:
Category : Ligands
Languages : en
Pages : 642
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Author: Justin C. Biffinger
Publisher:
ISBN:
Category : Complex compounds
Languages : en
Pages : 152
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Describes the synthesis and structure of mononuclear M(III) complexes and what factors control the stereochemistry.
