Lewis Basicity and Affinity Scales Data and Measurement

by Laurence, Christian; Gal, Jean-Franç ois

• ISBN13: 9780470749579
• ISBN10: 0470749571
• eBook ISBN(s): 9780470681893
• Edition: 1st
• Format: Hardcover
• Copyright: 2010-02-01
• Publisher: Wiley

Summary

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. Topics covered include:Lewis basicity and affinity measurements: definitions and context. the Donor Number or SbCl 5 affinity scale. the BF 3 affinity scale. thermodynamic and spectroscopic scales of hydrogen-bond basicity. thermodynamic and spectroscopic scales of halogen-bond basicity. gas-phase cation basicity and affinity scales. the measurement of Lewis basicity and affinity in the laboratoryThis 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.

Author Biography

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.

Table of Contents

Preface

Lewis basicity and affinity measurement: definitions and context

The Brönsted definition of acids and bases

Scales of Brönsted basicity and affinity in solution

Scales of Brönsted basicity and affinity in the gas phase

The Lewis definition of acids and bases

Quantum chemical descriptions of Lewis acid-base complexes

Measurement of Lewis basicity

Measurement of Lewis affinity

The role of the solvent

Spectroscopic scales of basicity (affinity)

Polybasic compounds

Attempts at a quantitative formulation of the Lewis definition of acids and bases

Concluding remarks and contents of Chapters 2-7

References

The Donor Number or SbCl₅ affinity scale

Structure of SbCl₅ complexes

Definition of the Donor Number scale

Experimental determination of the Donor Number

The Donor Number scale: data

Critical discussion

References

The BF₃ affinity scale

Structure of BF₃ complexes

Definition of the BF₃ affinity scale

Experimental determination of the BF₃ affinity scale

The BF₃ affinity scale: data

Discussion

Conclusion

References

Thermodynamic and spectroscopic scales of hydrogen-bond basicity and affinity

Structure of hydrogen-bonded complexes

Hydrogen-bond basicity scales. Early works

The 4-fluorophenol basicity scale

Hydrogen-bond affinity scales. Early works

The 4-fluorophenol affinity scale

Comparison of 4-fluorophenol affinity and basicity scales

Spectroscopic scales

Conclusion

References

Thermodynamic and spectroscopic scales of halogen-bond basicity and affinity

Structure of halogen-bonded complexes

The diiodine basicity scale

Is the diiodine basicity scale a general halogen-bond basicity scale?

The diiodine affinity scale

Spectroscopic scales

Conclusion

References

Gas-phase cation basicity and affinity scales

Cations as Lewis acids in the gas phase

Structure of cation/molecule adducts

Experimental techniques for measuring gas-phase cation affinities and basicities

Ion thermochemistry conventions

Lithium, sodium, potassium, aluminum, manganese, cyclopentadienylnickel, copper and methylammonium cation affinity and basicity scales

Significance and comparison of gas-phase cation scales

References

The measurement of Lewis basicity and affinity in the laboratory

Calorimetric determination of the BF₃ affinity of pyridine by gas/liquid reaction

Calorimetric determination of the BF₃ affinity of pyridine by liquid/liquid reaction

Determination by FTIR spectrometry of the complexation constants of 4-fluorophenol with isopropyl methyl ketone and progesterone

Determination by FTIR spectrometry of the complexation enthalpy and entropy of 4-fluorophenol with cyclopropylamine

FTIR determination of the OH shift of methanol hydrogen-bonded to pyridine, mesitylene and N-methylmorpholine

Solvatochromic shifts of 4-nitrophenol upon hydrogen bonding to nitriles

Determination by visible spectrometry of the complexation constant of diiodine with iodocyclohexane

Determination by visible spectrometry of the complexation enthalpy and entropy of diiodine with dimethyl sulfoxide

FTIR determination of the shift of the I-C stretching frequency of iodine cyanide upon halogen bonding to phosphine chalcogenides

Blue shift of the visible diiodine band upon halogen bonding to pyridines

Mass spectrometric determination of the gas-phase lithium cation basicity of dimethyl sulfoxide and methyl phenyl sulfoxide by the kinetic method

References

Index

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