Lewis Basicity And Affinity Scales

The Lewis concept of acids and bases is discussed in every general, organic and inorganic chemistry textbook. This is usually just a descriptive treatment, as it is not possible to devise a single numerical scale suitable for all occasions. However quantitative Lewis acid-base chemistry can be developed by compiling reaction-specific basicity scales which can be used in specific branches of chemistry and biochemistry. Lewis Basicity and Affinity Scales: Data and Measurementbrings together for the first time a comprehensive range of Lewis basicity/affinity data in one volume. More than 2400 equilibrium constants of acid-base reactions, 1500 complexation enthalpies, and nearly 2000 infrared and ultraviolet shifts upon complexation are gathered together in 25 thermodynamic and spectroscopic scales of basicity and/or affinity. For each scale, the definition, the method of measurement, an exhaustive database, and a critical discussion are given. All the data have been critically examined; some have been re-measured; literature gaps have been filled by original measurements; and each scale has been made homogeneous. This collection of data will enable experimental chemists to better understand and predict the numerous chemical, physical and biological properties that depend upon Lewis basicity. Chemometricians will be able to apply their methods to the data matrices constructed from this book in order to identify the factors which influence basicity and basicity-dependent properties. In addition, measured experimental basicities and affinities are essential to computational chemists for the validation, calibration and establishment of reliable computational methods for quantifying and explaining intermolecular forces and the chemical bond. Lewis Basicity and Affinity Scales: Data and Measurement is an essential single-source desktop reference for research scientists, engineers, and students in academia, research institutes and industry, in all areas of chemistry from fundamental to applied research. "The book is a noteworthy piece of work and represents a timely and vast accumulation of knowledge regarding Lewis bases that brings together accurate thermodynamic and spectroscopic data on typical reference Lewis acids. As such, it should serve as a useful and general guide to basicity." J. AM. CHEM. SOC. 2011, 133, 642

Acids and bases are ubiquitous in chemistry. Our understanding of them, however, is dominated by their behaviour in water. Transfer to non-aqueous solvents leads to profound changes in acid-base strengths and to the rates and equilibria of many processes: for example, synthetic reactions involving acids, bases and nucleophiles; isolation of pharmaceutical actives through salt formation; formation of zwitter- ions in amino acids; and chromatographic separation of substrates. This book seeks to enhance our understanding of acids and bases by reviewing and analysing their behaviour in non-aqueous solvents. The behaviour is related where possible to that in water, but correlations and contrasts between solvents are also presented. Fundamental background material is provided in the initial chapters: quantitative aspects of acid-base equilibria, including definitions and relationships between solution pH and species distribution; the influence of molecular structure on acid strengths; and acidity in aqueous solution. Solvent properties are reviewed, along with the magnitude of the interaction energies of solvent molecules with (especially) ions; the ability of solvents to participate in hydrogen bonding and to accept or donate electron pairs is seen to be crucial. Experimental methods for determining dissociation constants are described in detail. In the remaining chapters, dissociation constants of a wide range of acids in three distinct classes of solvents are discussed: protic solvents, such as alcohols, which are strong hydrogen-bond donors; basic, polar aprotic solvents, such as dimethylformamide; and low-basicity and low polarity solvents, such as acetonitrile and tetrahydrofuran. Dissociation constants of individual acids vary over more than 20 orders of magnitude among the solvents, and there is a strong differentiation between the response of neutral and charged acids to solvent change. Ion-pairing and hydrogen-bonding equilibria, such as between phenol and phenoxide ions, play an increasingly important role as the solvent polarity decreases, and their influence on acid-base equilibria and salt formation is described.

This three-volume set represents the first comprehensive coverage of the rapidly expanding field of Lewis base catalysis that has attracted enormous attention in recent years. Lewis base catalysis is a conceptually novel paradigm that encompasses an extremely wide variety of preparatively useful transformations and is particularly effective for enantioselectively constructing new stereogenic centers. As electron-pair donors, Lewis bases can influence the rate and stereochemical course of myriad synthetic organic reactions. The book presents the conceptual/mechanistic principles that underlie Lewis base catalysis, and then builds upon that foundation with a thorough presentation of many different reaction types. And last but not least, the editors, Prof. Edwin Vedejs and Prof. Scott E. Denmark, are without doubt the leaders in this emerging field and have compiled high quality contributions from an impressive collection of international experts.

This three-volume set represents the first comprehensive coverage of the rapidly expanding field of Lewis base catalysis that has attracted enormous attention in recent years. Lewis base catalysis is a conceptually novel paradigm that encompasses an extremely wide variety of preparatively useful transformations and is particularly effective for enantioselectively constructing new stereogenic centers. As electron-pair donors, Lewis bases can influence the rate and stereochemical course of myriad synthetic organic reactions. The book presents the conceptual/mechanistic principles that underlie Lewis base catalysis, and then builds upon that foundation with a thorough presentation of many different reaction types. And last but not least, the editors, Prof. Edwin Vedejs and Prof. Scott E. Denmark, are without doubt the leaders in this emerging field and have compiled high quality contributions from an impressive collection of international experts.

With the power and range of modern pulse spectrometers the compass of NMR spec troscopy is now very large for a single book-but we have undertaken this. Our book covers the Periodic Table as multinuclear spectrometers do, and introductory chapters are devoted to the essentials of the NMR experiment and its products. Primary products are chemical shifts (including anisotropies), spin-spin coupling constants, and relaxation times; the ultimate product is a knowledge of content and constitution, dynamic as well as static. Our province is chemical and biochemical rather than physical or technical; only passing reference is made to metallic solids or unstable species, or to practical NMR spectroscopy. Our aim is depth as well as breadth, to explain the fundamental processes, whether of nuclear magnetic shielding, spin-spin coupling, relaxation, or the multiple pulse sequences that have allowed the development of high-resolution studies of solids, multidimensional NMR spectroscopy, techniques for sensitivity enhancement, and so on. This book therefore combines the functions of advanced textbook and reference book. For reasonably comprehensive coverage in a single volume we have sum marized the information in tables and charts, and included all leading references.

Iodine Catalysis in Organic Synthesis The first book of its kind to highlight iodine as a sustainable alternative to conventional transition metal catalysis Iodine Catalysis in Organic Synthesis provides detailed coverage of recent advances in iodine chemistry and catalysis, focusing on the utilization of various iodine-containing compounds as oxidative catalysts. Featuring contributions by an international panel of leading research chemists, this authoritative volume explores the development of environmentally benign organic reactions and summarizes catalytic transformations of molecular iodine and iodine compounds such as hypervalent organoiodine and inorganic iodine salts. Readers are first introduced to the history of iodine chemistry, the conceptual background of homogeneous catalysis, and the benefits of iodine catalysis in comparison with transition metals. Next, chapters organized by reaction type examine enantioselective transformations, catalytic reactions involving iodine, catalyst states, oxidation in iodine and iodine catalyses, and catalytic reactions based on halogen bonding. Practical case studies and real-world examples of different applications in organic synthesis and industry are incorporated throughout the text. An invaluable guide for synthetic chemists in both academic and industrial laboratories, Iodine Catalysis in Organic Synthesis: Provides a thorough overview of typical iodine-catalyzed reactions, catalyst systems, structures, and reactivity Explores promising industrial applications of iodine-based reagents for organic synthesis Highlights the advantages iodine catalysis has over classical metal-catalyzed reactions Discusses sustainable and eco-friendly methods in hypervalent iodine chemistry Edited by two world authorities on the catalytic applications of organoiodine compounds, Iodine Catalysis in Organic Synthesis is required reading for catalytic, organic, and organometallic chemists, medicinal and pharmaceutical chemists, industrial chemists, and academic researchers and advanced students in relevant fields.