Tautomerism

Covering the gap between basic textbooks and over-specialized scientific publications, this is the first reference available to describe this interdisciplinary topic for PhD students and scientists starting in the field. The result is an introductory description providing suitable practical examples of the basic methods used to study tautomeric processes, as well as the theories describing the tautomerism and proton transfer phenomena. It also includes different spectroscopic methods for examining tautomerism, such as UV-VIs, time-resolved fluorescence spectroscopy, and NMR spectroscopy, plus the theoretical and practical background information. With its excellent overview of the methods, theories and examples, this is the perfect guide for any scientist dealing with tautomeric compounds in a wider context.

Covering the gap between basic textbooks and over-specialized scientific publications, this is the first reference available to describe this interdisciplinary topic for PhD students and scientists starting in the field.The result is an introductory description providing suitable practical examples of the basic methods used to study tautomeric processes, as well as the theories describing the tautomerism and proton transfer phenomena. It also includes different spectroscopic methods for examining tautomerism, such as UV-VIs, time-resolved fluorescence spectroscopy, and NMR spectroscopy, plus the theoretical and practical background information.With its excellent overview of the methods, theories and examples, this is the perfect guide for any scientist dealing with tautomeric compounds in a wider context.

PrefaceTAUTOMERISM: INTRODUCTIN, HISTORY, AND RECENT DEVELOPMENTS IN EXPERIMENTAL AND THEORETICAL METHODSThe Definition and Scope of Tautomerism: Principles and PracticalitiesCauses of Reversal in Tautomeric Form: Aromatic ResonanceCauses of Reversal in Tautomeric Form: Lone-Pair and Dipolar RepulsionCauses of Reversal in Tautomeric Form: Selective Stabilization Through "Far" Intramolecular Hydrogen BondingChanges in Tautomeric Form Brought About by Electronegative SubstituentsThe Influence of Solvent on Tautomeric FormTautomeric Equilibrium: Historical Overview of an Analytical ProblemShort Historical Overview of Tautomerization DynamicsConclusions and OutlookABSORPTION UV-vis SPECTROSCOPY AND CHEMOMETRICS: FROM QUALITATIVE CONCLUSIONS TO QUANTITATIVE ANALYSISIntroductionQuantitative Analysis of Tautomeric EquilibriaAnalysis of Real Tautomeric SystemsConcluding RemarksSTUDIES OF PHOTOINDUCED NH TAUTOMERISM BY STATIONARY AND TIME-RESOLVED FLUORESCENCE TECHNIQUESIntroductionPhotoinduced Proton/Hydrogen Atom TransferFluorescence Techniques for Studying TautomerismTautomerism in Bifunctional NH/N AzaaromaticsAb initio and DFT Computational MethodsNH Tautomerism as a Tool in BiophysicsConcluding RemarksFEMTOSECOND PUMP-PROBE SPECTROSCOPY OF PHOTOINDUCED TAUTOMERISMIntroductionUltrafast Pump-Probe SpectroscopyDynamics from Pump-Probe SpectroscopyReaction MechanismReaction-Path-Specific Wavepacket Dynamics in Double ESIPTInternal ConversionSummary and ConclusionsNMR SPECTROSCOPY STUDY OF TAUTOMERISM IN SOLUTION AND IN THE SOLID STATEIntroductionMethodologies of NMR Spectroscopy to Study TautomerismTypes of Tautomerism Studied by NMR SpectroscopyConclusions and OutlookISOTOPE EFFECTS ON CHEMICAL SHIFTS AS A TOOL IN THE STUDY OF TAUTOMERIC EQUILIBRIAIntroductionExperimental RequirementsIsotope Effects on Chemical ShiftsSecondary Equilibrium Isotope Effects on CSPrimary Isotope EffectsSolid StateTheoretical CalculationsExamplesOverviewTAUTOMER-SELECTIVE SPECTROSCOPY OF NUCLEOBASES, ISOLATED IN THE GAS PHASEIntroductionTechniquesGuanineAdenineCytosineUracil and ThymineBase PairsOutlookDIRECT EVIDENCE OF SOLID-STATE TAUTOMERISM BY DIFFRACTION METHODSD: ISOMERS, EQUILIBRIA, AND KINETICSApplication of X-Ray Diffraction to Study TautomerismExamples of X-Ray Diffraction Analysis of Proton TransferOther Diffraction Methods Used to Study Proton Transfer ReactionsDYNAMICS OF GROUND- AND EXCITED-STATE INTRAMOLECULAR PROTON TRANSFER REACTIONSIntroductionTransition State TheoryTwo Examples of TautomerizationThe Role of the SolventSolvent Friction and Solvent DynamicsThe Solvent Coordinate: BasicsPolarization FluctuationsThe Solvent Coordinate: An ApplicationElectronic RearrangementThe Rug that Ties the (Classical) Room TogetherQuantum and ClassicalQuantum DecayCoupling Quantum and Classical Motion: A Simple ExampleNonlinear OpticsFemtochemistryConcluding RemarksFORCE FIELD TREATMENT OF PROTON AND HYDROGEN TRANSFER IN MOLECULAR SYSTEMSIntroductionComputational Approaches to Proton TransferProton Transfer Reactions with MMPTApplications of MMPTDiscussion and OutlookTHE SCOPE AND LIMITATIONS OF LSER IN THE STUDY OF TAUTOMER RATIOIntroductionThe Taft-Kamlet LSER MethodologyLSER Case Histories in the Field of TautomerismOverviewTHE "BASICITY METHOD" FOR ESTIMATING TAUTOMER RATIO: A RADICAL RE-APPRAISALIntroductionExperimental ProtocolThe Derivation of Correction FactorsRegularities Revealed by Correction FactorsComplicating Factors in the Use of the "Basicity Method"Tautomeric Problems to Which the "Basicity Method" Is InapplicableOverviewQUANTUM CHEMICAL CALCULATION OF TAUTOMERIC EQUILIBRIAIntroductionComputational ProceduresSolvent EffectsApplications of Quantum Chemical Methods to Tautomeric EquilibriaConcluding RemarksIndex