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Lewis Basicity and Affinity Scales: Data and Measurement / Edition 1

Lewis Basicity and Affinity Scales: Data and Measurement / Edition 1

by Christian Laurence, Jean-Francois Gal


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Product Details

ISBN-13: 9780470749579
Publisher: Wiley
Publication date: 02/09/2010
Pages: 476
Product dimensions: 6.70(w) x 9.80(h) x 1.20(d)

About the Author

Professor Christian Laurence, UFR Sciences et Techniques, UMR CEISAM 6230 CNRS-Université de Nantes, France
Christian Laurence is Professor Emeritus of Chemistry at the University of Nantes. He was head of the laboratory of spectrochemistry of the Faculty of Sciences of Nantes for 23 years, where he published more than 140 scientific papers in the field of physical organic chemistry.

Professor Jean-François Gal, Laboratoire de Radiochimie, Sciences Analytiques et Environnement, Institut de Chimie de Nice (FR CNRS 3037), Université de Nice-Sophia Antipolis- Parc Valrose, France
Jean-François Gal is Professor Emeritus of Chemistry at the University of Nice-Sophia Antipolis. He supervised, for more than 25 years, a group working on mass spectrometry and, specifically, on ion/molecule reactions, gas-phase acidity and basicity, and metal cation reactions.

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Table of Contents


1 Lewis Basicity and Affinity Measurement: Definitions andContext.

1.1 The Brönsted Definition of Acids and Bases.

1.2 Scales of Brönsted Basicity and Affinity inSolution.

1.3 Scales of Brönsted Basicity and Affinity in the GasPhase.

1.4 The Lewis Definition of Acids and Bases.

1.5 Quantum Chemical Descriptions of Lewis Acid/BaseComplexes.

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 LewisDefinition of Acids and Bases.

1.12 Concluding Remarks and Content of Chapters 2–7.


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.


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 AffinityScale.

3.4 The BF3 Affinity Scale: Data.

3.5 Discussion.

3.6 Conclusion.


4 Thermodynamic and Spectroscopic Scales of Hydrogen-BondBasicity 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 BasicityScales.

4.7 Spectroscopic Scales.

4.8 Conclusion.


5 Thermodynamic and Spectroscopic Scales of Halogen-BondBasicity and Affinity.

5.1 Structure of Halogen-Bonded Complexes.

5.2 The Diiodine Basicity Scale.

5.3 Is the Diiodine Basicity Scale a General Halogen-BondBasicity Scale?.

5.4 The Diiodine Affinity Scale.

5.5 Spectroscopic Scales.

5.6 Conclusion.


6 Gas-Phase Cation Affinity and Basicity Scales.

6.1 Cations as Lewis Acids in the Gas Phase.

6.2 Structure of Cation/Molecule Adducts.

6.3 Experimental Techniques for Measuring Gas-Phase CationAffinities and Basicities.

6.4 Ion Thermochemistry Conventions.

6.5 Lithium, Sodium, Potassium, Aluminium, Manganese,Cyclopentadienylnickel, Copper and Methylammonium Cations Affinityand Basicity Scales.

6.6 Significance and Comparison of Gas-Phase Cation Scales.


7 The Measurement of Lewis Basicity and Affinity in theLaboratory.

7.1 Calorimetric Determination of the BF3 Affinity ofPyridine by Gas/Liquid Reaction.

7.2 Calorimetric Determination of the BF3 Affinity ofPyridine by Liquid/Liquid Reaction.

7.3 Determination by FTIR Spectrometry of the ComplexationConstants of 4-Fluorophenol with Isopropyl Methyl Ketone andProgesterone.

7.4 Determination by FTIR Spectrometry of the ComplexationEnthalpy and Entropy of 4-Fluorophenol with Cyclopropylamine.

7.5 FTIR Determination of the OH Shift of Methanol HydrogenBonded to Pyridine, Mesitylene and N-Methylmorpholine.

7.6 Solvatochromic Shifts of 4-Nitrophenol upon Hydrogen Bondingto Nitriles.

7.7 Determination of the Complexation Constant of Diiodine withIodocyclohexane by Visible Spectrometry.

7.8 Determination of the Complexation Enthalpy and Entropy ofDiiodine with Dimethyl Sulfoxide by Visible Spectrometry.

7.9 FTIR Determination of the Shift of the I C Stretching ofIodine Cyanide upon Halogen Bonding to Phosphine Chalcogenides.

7.10 Blue Shift of the Visible Diiodine Transition Upon HalogenBonding to Pyridines.

7.11 Mass Spectrometric Determination of the Gas-Phase LithiumCation Basicity of Dimethyl Sulfoxide and Methyl Phenyl Sulfoxideby the Kinetic Method.



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"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." (JACS, February 2011)

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