Lewis basicity and affinity scales : data and measurement /
Lewis Basicity and Affinity Scales provides 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 th...
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| Format: | eBook |
| Language: | English |
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Hoboken, N.J. :
Wiley,
2009.
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| Series: | Wiley online library.
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| Subjects: | |
| Online Access: | Connect to the full text of this electronic book |
Table of Contents:
- Cover
- Title Page
- Copyright Page
- Table of Contents
- Preface
- 1 Lewis Basicity and Affinity Measurement: Definitions and Context
- 1.1 The Br168;onsted Definition of Acids and Bases
- 1.2 Scales of Br168;onsted Basicity and Affinity in Solution
- 1.3 Scales of Br168;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 Molecules
- 1.6 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 Scales
- 1.12 Concluding Remarks and Content of Chapters 28230;7
- References
- 2 The Donor Number or SbCI5 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 BF3
- 3.5.3 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 Scale
- 4.6 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?
- 5.4 The Diiodine Affinity Scale
- 5.5 Spectroscopic Scales
- 5.5.1 Infrared Shifts of ICN, I2 and ICl
- 5.5.2 The Blue Shift of the Diiodine Visible Band
- 5.6 Conclusion.