Lewis basicity and affinity scales : data and measurement / / Christian Laurence, Jean-Franc ois Gal

• Record Nr.: UNINA9910877696703321
• Autore: Laurence Christian
• Pubbl/distr/stampa: Chichester, : Wiley, 2010
• ISBN: 1-282-68724-7; 9786612687242; 0-470-68190-X; 0-470-68189-6
• Descrizione fisica: 1 online resource (490 p.)
• Altri autori (Persone): GalJean-Franc ois
• Disciplina: 541.39; 541.395; 546.24
• Soggetti: Lewis acids; Chemistry
• Lingua di pubblicazione: Inglese
• Formato: Materiale a stampa
• Livello bibliografico: Monografia
• Note generali: Description based upon print version of record.
• Nota di contenuto: Lewis Basicity and Affinity Scales; Contents; Preface; 1 Lewis Basicity and Affinity Measurement: Definitions and Context; 1.1 The Br ̈onsted Definition of Acids and Bases; 1.2 Scales of Br ̈onsted Basicity and Affinity in Solution; 1.3 Scales of Br ̈onsted 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; 1.5.1 Valence-Bond Model; 1.5.2 Perturbation Molecular Orbital Theory; 1.5.3 Variational Supermolecular Method and Energy Decomposition Schemes; 1.5.4 Natural Bond Orbital Theory; 1.5.5 Quantum Theory of Atoms in Molecules1.6 Measurement of Lewis Basicity; 1.6.1 Gas-phase Reactions; 1.6.2 Solution Reactions; 1.6.3 Standard State Transformations; 1.6.4 Choice of Solvent; 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; 1.11.1 Hard and Soft Acids and Bases; 1.11.2 The ECW and ECT Models; 1.11.3 The Beta and Xi Equation; 1.11.4 A ; Chemometric Approach; 1.11.5 Quantum Chemical Descriptors for Basicity Scales1.12 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 The BF3 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; 3.5.1 Medium Effects; 3.5.2 Hardness of BF33.5.3 Comparison of the BF3 and SbCl5 Affinity Scales; 3.5.4 Computation of the BF3 Affinity; 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; 4.3.1 Definition; 4.3.2 Method of Determination; 4.3.3 Polyfunctional Hydrogen-Bond Acceptors; 4.3.4 Data; 4.3.5 Range of Validity of the Scale; 4.4 Hydrogen-Bond Affinity Scales: Early Studies; 4.5 The 4-Fluorophenol Affinity Scale4.6 Comparison of 4-Fluorophenol Affinity and Basicity Scales; 4.7 Spectroscopic Scales; 4.7.1 Infrared Shift of Methanol; 4.7.2 Solvatochromic Shifts of 4-Nitrophenol and 4-Nitroaniline; 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; 5.2.1 Definition of the Scale; 5.2.2 Methods for the Determination of Diiodine Complexation Constants; 5.2.3 Temperature Correction; 5.2.4 Solvent Effects; 5.2.5 Data; 5.3 Is the Diiodine Basicity Scale a General Halogen-Bond Basicity Scale?
• Sommario/riassunto: 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 t