Lewis Basicity and Affinity Scales (eBook)

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.

Preface

Chapter 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 contents of Chapters 2-7

References

Chapter 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

Chapter 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

3.6 Conclusion

References

Chapter 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 basicity scale

4.4 Hydrogen-bond affinity scales. Early works

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

Chapter 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 general halogen-bond basicity scale?

5.4 The diiodine affinity scale

5.5 Spectroscopic scales

5.6 Conclusion

References

Chapter 6 Gas-phase cation basicity and affinity 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 cation affinities and basicities

6.4 Ion thermochemistry conventions

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

6.6 Significance and comparison of gas-phase cation scales

References

Chapter 7 The measurement of Lewis basicity and affinity in the laboratory

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

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

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

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

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

7.6 Solvatochromic shifts of 4-nitrophenol upon hydrogen bonding to nitriles

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

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

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

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

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

References

Index