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. This 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. "e;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."e; J. AM. CHEM. SOC. 2011, 133, 642

The Lewis concept of acids and bases is discussed in every generalorganic 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 scalethe definition, the method of measurement, an exhaustive databaseand 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

PrefaceChapter 1 Lewis basicity and affinity measurement: definitions and context1.1 The Brönsted definition of acids and bases1.2 Scales of Brönsted basicity and affinity in solution1.3 Scales of Brönsted basicity and affinity in the gas phase1.4 The Lewis definition of acids and bases1.5 Quantum chemical descriptions of Lewis acid-base complexes1.6 Measurement of Lewis basicity1.7 Measurement of Lewis affinity1.8 The role of the solvent1.9 Spectroscopic scales of basicity (affinity)1.10 Polybasic compounds1.11 Attempts at a quantitative formulation of the Lewis definition of acids and bases1.12 Concluding remarks and contents of Chapters 2-7ReferencesChapter 2 The Donor Number or SbCl5 affinity scale2.1 Structure of SbCl5 complexes2.2 Definition of the Donor Number scale2.3 Experimental determination of the Donor Number2.4 The Donor Number scale: data2.5 Critical discussionReferencesChapter 3 The BF3 affinity scale3.1 Structure of BF3 complexes3.2 Definition of the BF3 affinity scale3.3 Experimental determination of the BF3 affinity scale3.4 The BF3 affinity scale: data3.5 Discussion3.6 ConclusionReferencesChapter 4 Thermodynamic and spectroscopic scales of hydrogen-bond basicity and affinity4.1 Structure of hydrogen-bonded complexes4.2 Hydrogen-bond basicity scales. Early works4.3 The 4-fluorophenol basicity scale4.4 Hydrogen-bond affinity scales. Early works4.5 The 4-fluorophenol affinity scale4.6 Comparison of 4-fluorophenol affinity and basicity scales4.7 Spectroscopic scales4.8 ConclusionReferencesChapter 5 Thermodynamic and spectroscopic scales of halogen-bond basicity and affinity5.1 Structure of halogen-bonded complexes5.2 The diiodine basicity scale5.3 Is the diiodine basicity scale a general halogen-bond basicity scale?5.4 The diiodine affinity scale5.5 Spectroscopic scales5.6 ConclusionReferencesChapter 6 Gas-phase cation basicity and affinity scales6.1 Cations as Lewis acids in the gas phase6.2 Structure of cation/molecule adducts6.3 Experimental techniques for measuring gas-phase cation affinities and basicities6.4 Ion thermochemistry conventions6.5 Lithium, sodium, potassium, aluminum, manganese, cyclopentadienylnickel, copper and methylammonium cation affinity and basicity scales6.6 Significance and comparison of gas-phase cation scalesReferencesChapter 7 The measurement of Lewis basicity and affinity in the laboratory7.1 Calorimetric determination of the BF3 affinity of pyridine by gas/liquid reaction7.2 Calorimetric determination of the BF3 affinity of pyridine by liquid/liquid reaction7.3 Determination by FTIR spectrometry of the complexation constants of 4-fluorophenol with isopropyl methyl ketone and progesterone7.4 Determination by FTIR spectrometry of the complexation enthalpy and entropy of 4-fluorophenol with cyclopropylamine7.5 FTIR determination of the OH shift of methanol hydrogen-bonded to pyridine, mesitylene and N-methylmorpholine7.6 Solvatochromic shifts of 4-nitrophenol upon hydrogen bonding to nitriles7.7 Determination by visible spectrometry of the complexation constant of diiodine with iodocyclohexane7.8 Determination by visible spectrometry of the complexation enthalpy and entropy of diiodine with dimethyl sulfoxide7.9 FTIR determination of the shift of the I-C stretching frequency of iodine cyanide upon halogen bonding to phosphine chalcogenides7.10 Blue shift of the visible diiodine band upon halogen bonding to pyridines7.11 Mass spectrometric determination of the gas-phase lithium cation basicity of dimethyl sulfoxide and methyl phenyl sulfoxide by the kinetic methodReferencesIndex