Der Artikel wird am Ende des Bestellprozesses zum Download zur Verfügung gestellt.

Lewis Basicity and Affinity Scales

Data and Measurement
 E-Book
Sofort lieferbar | Lieferzeit:3-5 Tage I
ISBN-13:
9780470681893
Einband:
E-Book
Seiten:
476
Autor:
Christian Laurence
eBook Typ:
PDF
eBook Format:
E-Book
Kopierschutz:
Adobe DRM [Hard-DRM]
Sprache:
Englisch
Beschreibung:

The Lewis concept of acids and bases is discussed in every general,organic and inorganic chemistry textbook. This is usually just adescriptive treatment, as it is not possible to devise a singlenumerical scale suitable for all occasions. However quantitativeLewis acid-base chemistry can be developed by compilingreaction-specific basicity scales which can be used in specificbranches of chemistry and biochemistry.
Lewis Basicity and Affinity Scales: Data andMeasurementbrings together for the first time a comprehensiverange of Lewis basicity/affinity data in one volume. More than 2400equilibrium constants of acid-base reactions, 1500 complexationenthalpies, and nearly 2000 infrared and ultraviolet shifts uponcomplexation are gathered together in 25 thermodynamic andspectroscopic 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 beencritically examined; some have been re-measured; literature gapshave been filled by original measurements; and each scale has beenmade homogeneous.

This collection of data will enable experimental chemists tobetter understand and predict the numerous chemical, physical andbiological properties that depend upon Lewis basicity.Chemometricians will be able to apply their methods to the datamatrices constructed from this book in order to identify thefactors which influence basicity and basicity-dependent properties.In addition, measured experimental basicities and affinities areessential to computational chemists for the validation, calibrationand establishment of reliable computational methods for quantifyingand explaining intermolecular forces and the chemical bond.

Lewis Basicity and Affinity Scales: Data and Measurementis an essential single-source desktop reference for researchscientists, engineers, and students in academia, researchinstitutes and industry, in all areas of chemistry from fundamentalto applied research.

"The book is a noteworthy piece of work and represents atimely and vast accumulation of knowledge regarding Lewis basesthat brings together accurate thermodynamic and spectroscopicdata on typical reference Lewis acids. As such, it should serve asa useful and general guide to basicity." J. AM. CHEM.SOC. 2011, 133, 642
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

Kunden Rezensionen

Zu diesem Artikel ist noch keine Rezension vorhanden.
Helfen sie anderen Besuchern und verfassen Sie selbst eine Rezension.