Lewis Basicity and Affinity Scales: Data and Measurement

Lewis Basicity and Affinity Scales......Page 5
Contents......Page 9
Preface......Page 15
1 Lewis Basicity and Affinity Measurement: Definitions and Context......Page 19
1.1 The Brönsted Definition of Acids and Bases......Page 20
1.2 Scales of Brönsted Basicity and Affinity in Solution......Page 21
1.4 The Lewis Definition of Acids and Bases......Page 24
1.5.2 Perturbation Molecular Orbital Theory......Page 28
1.5.3 Variational Supermolecular Method and Energy Decomposition Schemes......Page 30
1.5.4 Natural Bond Orbital Theory......Page 35
1.5.5 Quantum Theory of Atoms in Molecules......Page 36
1.6 Measurement of Lewis Basicity......Page 38
1.6.1 Gas-phase Reactions......Page 39
1.6.2 Solution Reactions......Page 40
1.6.3 Standard State Transformations......Page 41
1.7 Measurement of Lewis Affinity......Page 42
1.8 The Role of the Solvent......Page 47
1.9 Spectroscopic Scales of Basicity (Affinity)......Page 52
1.10 Polybasic Compounds......Page 56
1.11.1 Hard and Soft Acids and Bases......Page 60
1.11.2 The ECW and ECT Models......Page 65
1.11.3 The Beta and Xi Equation......Page 70
1.11.4 A Chemometric Approach......Page 71
1.11.5 Quantum Chemical Descriptors for Basicity Scales......Page 74
1.12 Concluding Remarks and Content of Chapters 2–7......Page 76
References......Page 78
2.1 Structure of SbCl5 Complexes......Page 89
2.3 Experimental Determination of the Donor Number......Page 91
2.4 The Donor Number Scale: Data......Page 92
2.5 Critical Discussion......Page 98
References......Page 99
3 The BF3 Affinity Scale......Page 103
3.1 Structure of BF3 Complexes......Page 104
3.2 Definition of the BF3 Affinity Scale......Page 106
3.3 Experimental Determination of the BF3 Affinity Scale......Page 107
3.4 The BF3 Affinity Scale: Data......Page 108
3.5.2 Hardness of BF3......Page 120
3.5.3 Comparison of the BF3 and SbCl5 Affinity Scales......Page 121
3.5.4 Computation of the BF3 Affinity......Page 122
3.6 Conclusion......Page 123
References......Page 124
4 Thermodynamic and Spectroscopic Scales of Hydrogen-Bond Basicity and Affinity......Page 129
4.1 Structure of Hydrogen-Bonded Complexes......Page 131
4.2 Hydrogen-Bond Basicity Scales: Early Works......Page 135
4.3.2 Method of Determination......Page 137
4.3.3 Polyfunctional Hydrogen-Bond Acceptors......Page 138
4.3.4 Data......Page 139
4.3.5 Range of Validity of the Scale......Page 185
4.4 Hydrogen-Bond Affinity Scales: Early Studies......Page 186
4.5 The 4-Fluorophenol Affinity Scale......Page 188
4.6 Comparison of 4-Fluorophenol Affinity and Basicity Scales......Page 203
4.7.1 Infrared Shift of Methanol......Page 206
4.7.2 Solvatochromic Shifts of 4-Nitrophenol and 4-Nitroaniline......Page 228
References......Page 239
5 Thermodynamic and Spectroscopic Scales of Halogen-Bond Basicity and Affinity......Page 247
5.1 Structure of Halogen-Bonded Complexes......Page 249
5.2.1 Definition of the Scale......Page 255
5.2.2 Methods for the Determination of Diiodine Complexation Constants......Page 256
5.2.4 Solvent Effects......Page 257
5.2.5 Data......Page 261
5.3 Is the Diiodine Basicity Scale a General Halogen-Bond Basicity Scale?......Page 301
5.4 The Diiodine Affinity Scale......Page 303
5.5.1 Infrared Shifts of ICN, I2 and ICl......Page 304
5.5.2 The Blue Shift of the Diiodine Visible Band......Page 324
References......Page 327
6.1 Cations as Lewis Acids in the Gas Phase......Page 341
6.2 Structure of Cation/Molecule Adducts......Page 344
6.3.1 High-Pressure Mass Spectrometry (HPMS)......Page 352
6.3.2 Collision-Induced Dissociation Threshold (CIDT)......Page 353
6.3.3 Ligand-Exchange Equilibrium Measurements in Trapping Devices......Page 354
6.3.5 Kinetic Method......Page 355
6.3.7 Blackbody Infrared Radiative Dissociation (BIRD)......Page 356
6.4 Ion Thermochemistry Conventions......Page 357
6.5.1 Lithium......Page 358
6.5.2 Sodium......Page 364
6.5.3 Potassium......Page 371
6.5.5 Manganese......Page 372
6.5.6 Cyclopentadienylnickel......Page 378
6.5.7 Copper......Page 384
6.5.8 Methylammonium......Page 389
6.6.1 Properties of Cations and Significance of MCB and MCA Scales......Page 394
6.6.2 Relationship of MCA with MCB......Page 399
6.6.3 The Computation of MCB and MCA Scales......Page 400
6.6.4 MCA and MCB Scales and the Concept of a Cation/  Interaction......Page 401
6.6.5 Conventional Versus Ionic Hydrogen-Bond Basicity and Affinity Scales......Page 404
6.6.6 Comparison of Cation Basicity Scales......Page 405
References......Page 407
7.1.1 Introduction: Principles and Difficulties in the Calorimetric Measurement of the Enthalpy of a Gas/Liquid Reaction......Page 419
7.1.2 Reagents and Equipment......Page 421
7.1.3 Experiment......Page 422
7.1.4 Results......Page 423
7.2.1 Introduction: Measuring Relative BF3 Affinity by Ligand Exchange in Solution......Page 424
7.2.4 Results......Page 425
7.3.1 Introduction: Recognition of Progesterone by its Receptor......Page 426
7.3.3 Experiment......Page 427
7.3.4 Results and Discussion......Page 428
7.4.1 Introduction......Page 431
7.4.4 Results......Page 432
7.4.5 Comparison with Theoretical Calculations......Page 435
7.5.2 Reagents and Equipment......Page 436
7.5.4 Results and Discussion......Page 437
7.6.1 Introduction......Page 438
7.6.3 Experiment......Page 439
7.6.4 Results and Discussion......Page 440
7.7.2 The Rose–Drago Method......Page 442
7.7.4 Experiment......Page 444
7.7.5 Results and Discussion: Illustration of the HSAB Principle......Page 445
7.8.3 Experiment......Page 447
7.8.4 Results......Page 448
7.8.5 Discussion......Page 450
7.9.1 Introduction......Page 452
7.9.4 Results and Discussion: Δv(ICN) as a Spectroscopic Scale of Halogen-Bond Affinity......Page 453
7.10.1 Introduction......Page 454
7.10.3 Experiment......Page 455
7.10.4 Results and Discussion: Substituent Effects......Page 456
7.11.1 The Kinetic Method......Page 457
7.11.2 Reagents and Equipment......Page 458
7.11.3 Experiment......Page 459
7.11.4 Data Treatment......Page 460
7.11.5 Discussion: Substituent Effects......Page 462
References......Page 463
Index......Page 465
Color Plate......Page 479