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Organometallic Radical Processes

Organometallic Radical Processes
Author: William C. Trogler
Publisher: Elsevier Publishing Company
Total Pages: 402
Release: 1990
Genre: Science
ISBN:

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Odd electron organotransition metal complexes, once viewed as isolated exceptions to the 18-electron rule, are now recognized as a subset of compounds with unique reactivities. The identification of organometallic radicals as intermediates in the reaction mechanisms of even electron systems makes them increasingly important to the non-radical chemist as well. This book focuses on the generation, spectroscopic properties, structures, and reaction mechanisms exhibited by 17- and 19-electron organometallic complexes. The topics discussed center on transition metal complexes, although analogies to the chemistry of main group radicals are illustrated when appropriate. The material has been organized into ten self-contained chapters so that the reader can learn selectively about a particular area of interest. Two chapters focus on the techniques of electrochemistry and ESR spectroscopy, which are particularly suited to the study of organometallic radicals. Another chapter provides an overview of geometrical structrures for stable radicals.


Free Radicals in Chemistry and Biology

Free Radicals in Chemistry and Biology
Author: Milan Lazar
Publisher: CRC Press
Total Pages: 322
Release: 1989-03-31
Genre: Science
ISBN: 9780849353871

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Elementary radical reactions are described in terms of fundamental knowledge of organic chemistry and chemical physics in this valuable reference text. The complex radical processes of nonchain and chain mechanisms, such as dimerization, alkylation, polymerization, telomerization, halogenation pyrolysis, oxidation and combustion, are complemented by reactions in chemical lasers and in the cosmos, as well as by reactions in biological objects under normal or pathological metabolism. The text also provides the synthesis of facts from various fields of research and involves mechanisms where free radicals appear either as main or side intermediates in one of the several alternatives of the reaction pathway. Highlights include 38 tables and 39 figures.


Photoinduced Electron Transfer

Photoinduced Electron Transfer
Author: Marye Anne Fox
Publisher:
Total Pages: 820
Release: 1988
Genre: Science
ISBN: 9780444871251

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Electron transfer reactions are of great importance to nearly every subdiscipline of chemistry. The simple transfer of a single electron has been shown repeatedly to be a common activating mode for organic, inorganic, and biological molecules, and the very ubiquity of such reactions has guaranteed that their investigation would involve the most fundamental questions of modern chemistry. The fact that photoexcitation induces enhanced redox reactivity via electron transfer also provides a convenient method for experimentally testing theoretical predictions regarding structural and energetic effects. As can be seen from the very size of this work there is a great deal known about photoinduced electron transfer reactions and the editors have tried to capture the diversity and excitement inherent in this broad field. The reader will find contributions from theorists and experimentalists, from organic and inorganic chemists, from the perspective of the synthetic and mechanistic viewpoint. Some contributions are fundamental basic research, while others clearly show practical applications of these principles.These volumes are intended to serve a joint purpose: as a reference resource and an introductory overview to the diverse research accomplished via photoexcitation of electron donor-acceptor systems. The information is organized in four parts. The first deals with the theoretical and conceptual factors which influence electron transfer. The second covers experimental methodology and medium effects. The third and fourth deal with reactivity, with most organic transformation being addressed in Part C and most inorganic reactions covered in Part D. Each part thus provides an overview of typical reactions observed for these classes of compounds. Part D also provides examples of photoinduced electron transfer in current use in important applications. There is of course a significant interdependence between the four parts. Subject, chemical, and author citation indices appear at the end of each of Parts A, B and C, and comprehensive indices are included in Part D.


Photoprocesses in Transition Metal Complexes, Biosystems and Other Molecules. Experiment and Theory

Photoprocesses in Transition Metal Complexes, Biosystems and Other Molecules. Experiment and Theory
Author: E. Kochanski
Publisher: Springer Science & Business Media
Total Pages: 448
Release: 2012-12-06
Genre: Science
ISBN: 9401126984

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The scope of this paper is to recall fundamental notions of the molecular spectroscopy and dynamics, necessary for discussion of photophysical and photochemical processes in condensed phases. We will thus treat in a more detailed way the specific features which are important for molecular systems strongly interacting with their environment. Other aspects such as the time evolution of isolated molecules, single-level excitation and state-to-state chemistry, important for the gas-phase photophysics are omitted. We start (Sec.2) with a brief description of radiative processes (light absorption and emission) in molecules. In the quantum-mechanical treatment of this problem, the appropriate basis is that of so-called zero-order states, corresponding to the traditional scheme of electronic states (singlets, doublets, triplets etc.) and vibrational levels belonging to each state. The important point will be deduction of selection rules for most radiative transitions. At this stage all molecular states are considered as stationary states. In order to treat the breakdown of simple selection rules and non-radiative transitions between individual molecular states, it is necessary to take into account the mechanisms coupling the zero-order states (Sec.3). We will first focus on intramolecular coupling effects and then discuss the solvent effects on intramolecular relaxation processes. The problem of the non-radiative transfer of the electronic energy between different molecules - closely related to that of the energy dissipation within a single molecule will be treated in Sec.4.


Electron Transfer II

Electron Transfer II
Author: Jochen Mattay
Publisher: Springer
Total Pages: 216
Release: 1995-12-11
Genre: Science
ISBN: 9783540601104

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Ab Initio calculations on electron-transfer catalysis by metal ions; Photoreactions of metal complexes with DNA, especially those involving a primary photo-electron transfer; Radical ion cyclizations; One electron redox reactions between radicals and organic molecules - an addition/elemination (inner sphere) path; Antenna structure and energy transfer in higher plant photosystems.