Lewis Basicity and Affinity Scales

Christian Laurence 지음

Wiley 2009년 12월 23일 출간

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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 ar

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Preface.1 Lewis Basicity and Affinity Measurement: Definitions and Context.1.1 The Brönsted Definition of Acids and Bases.1.2 Scales of Brönsted Basicity and Affinity in Solution.1.3 Scales of Brönsted Basicity and Affinity in the Gas Phase.1.4 The Lewis Definition of Acids and Bases.1.5 Quantum Chemical Descriptions of Lewis Acid/Base Complexes.1.6 Measurement of Lewis Basicity.1.7 Measurement of Lewis Affinity.1.8 The Role of the Solvent.1.9 Spectroscopic Scales of Basicity (Affinity).1.10 Polybasic Compounds.1.11 Attempts at a Quantitative Formulation of the Lewis Definition of Acids and Bases.1.12 Concluding Remarks and Content of Chapters 2&~7.References.2 The Donor Number or SbCl5 Affinity Scale.2.1 Structure of SbCl5 Complexes.2.2 Definition of the Donor Number Scale.2.3 Experimental Determination of the Donor Number.2.4 The Donor Number Scale: Data.2.5 Critical Discussion.References.3 TheBF3 Affinity Scale.3.1 Structure of BF3 Complexes.3.2 Definition of the BF3 Affinity Scale.3.3 Experimental Determination of the BF3 Affinity Scale.3.4 The BF3 Affinity Scale: Data.3.5 Discussion.3.6 Conclusion.References.4 Thermodynamic and Spectroscopic Scales of Hydrogen-Bond Basicity and Affinity.4.1 Structure of Hydrogen-Bonded Complexes.4.2 Hydrogen-Bond Basicity Scales: Early Works.4.3 The 4-Fluorophenol Hydrogen-Bond Basicity Scale.4.4 Hydrogen-Bond Affinity Scales: Early Studies.4.5 The 4-Fluorophenol Affinity Scale.4.6 Comparison of 4-Fluorophenol Affinity and Basicity Scales.4.7 Spectroscopic Scales.4.8 Conclusion.References.5 Thermodynamic and Spectroscopic Scales of Halogen-Bond Basicity and Affinity.5.1 Structure of Halogen-Bonded Complexes.5.2 The Diiodine Basicity Scale.5.3 Is the Diiodine Basicity Scale a G

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저자(글) Christian Laurence