Reactivity and Thermochemistry of First-row Transition Metal Complexes with Stable Organic Radicals PDF Download
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Author: Thomas R. Porter Publisher: ISBN: Category : Languages : en Pages : 179
Book Description
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: Thomas R. Porter Publisher: ISBN: Category : Languages : en Pages : 179
Book Description
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: Louis S. Hegedus Publisher: University Science Books ISBN: 9781891389047 Category : Science Languages : en Pages : 358
Book Description
This second edition offers easy access to the field of organotransition metal chemistry. The book covers the basics of transition metal chemistry, giving a practical introduction to organotransition reaction mechanisms.
Author: Jon A. McCleverty Publisher: ISBN: 9780191992971 Category : Transition metals Languages : en Pages : 0
Book Description
'Chemistry of the First Row Transition Metals' introduces this field of chemistry. The reactivity and structural properties of first-row transition metals and their compounds depend on the electronic configuration of the d electrons of the metal. The book describes the most significant structures, reactions, and other important properties of co-ordination, organometallic and solid-state compounds, and also sketches the role of first-row transition metals in biology.
Author: Eleanor Crabb Publisher: ISBN: 9781849730624 Category : Science Languages : en Pages : 140
Book Description
The chemistry of the transition metals is a vital part of undergraduate courses in inorganic chemistry and is an essential background for bioinorganic chemistry. This teaching text, together with the accompanying Periodic Table DVD-ROM, provides an introduction to the transition metals, examining the behaviour of the metals and their aqueous ions and complexes. The book begins, largely using interactive activities and video on the DVD, by introducing the reader to the chemistry of the first-row transition elements in different oxidation states, in particular +2 and +3, and their relative stability. This is followed by a study of coordination chemistry. Later chapters look at theories of metal-ligand bonding and the way models can be used to rationalise many of the properties of transition metals and their compounds, such as colour, magnetism and stereochemistry. Starting with the simple, yet powerful crystal-field approach, the book finishes with a largely pictorial treatment of molecular orbital theory. (A basic knowledge of atomic and molecular orbitals as applied to the main-Group elements is assumed.) The material in this book is designed to be used either as part of an undergraduate chemistry programme, or for self-directed study. Learning is facilitated through various key features, including: "interactive activities on the accompanying Periodic Table DVD "in-text questions with answers "full-colour diagrams "revision exercises on an associated website (www.rsc.org/metalsandlife) This book was written as part of the teaching material for the Open University course, S347 Metals and Life. An associated book, Metals and Life also published by RSC Publishing, explores the vital role that metals play in the physiology of animals and plants, and increasingly in medicine.
Author: Jon McCleverty Publisher: OUP Oxford ISBN: 9780198501510 Category : Science Languages : en Pages : 100
Book Description
The transition metals titanium, vanadium, chromium, manganese, iron, cobalt, nickel and copper are essential for many life-processes, are at the heart of important industrial processes, and are used in everyday life. Their properties are dependent on the electronic structure of the metals. The connection between this and the chemical behaviour of these metals is described in this book.
Author: Michael Isaac Lipschutz Publisher: ISBN: Category : Languages : en Pages : 139
Book Description
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: Jiro Tsuji Publisher: ISBN: Category : Science Languages : en Pages : 504
Book Description
Transition Metal Reagents and Catalysts Innovations in Organic Synthesis Jiro Tsuji Emeritus Professor, Tokyo Institute of Technology, Japan Numerous innovative and practical synthetic methods using transition metal complexes as either catalysts or reagents have been developed over the last 35 years. Transition Metal Reagents and Catalysts combines the varied applications of transition metal complexes in a unique and timely book in this rapidly advancing area of organic synthesis. This text is an easily understandable and enjoyable read for organic chemists who are not yet familiar with organo-transition metal chemistry. Transition Metal Reagents and Catalysts presents: * Complete coverage of nearly 35 years of transition metal complex chemistry * An in-depth treatment of many innovative synthetic methodologies * A rational classification of all reactions according to substrates and reaction mechanisms * Examples of important applications of transition metal catalysed reactions. A knowledge of organic synthesis using transition metal complexes is a must for all synthetic organic chemists. Written for chemists who wish to apply novel synthetic methods using transition metal complexes to solve problems in organic and pharmaceutical chemistry, such as synthesis of fine and bulk chemicals and natural products, Transition Metal Reagents and Catalysts is an essential reference source and an indispensible research companion.
Author: Thomas R. Porter
Author: Thomas R. Porter
Author: Louis S. Hegedus
Author: Jon A. McCleverty
Author: David Nicholls
Author: Eleanor Crabb
Author: Jon McCleverty
Author: 
Author: Michael Isaac Lipschutz
Author: Jiro Tsuji
Author: Brenda Frazier