Tautomerism. Methods and Theories

  • ID: 2329800
  • Book
  • 400 Pages
  • John Wiley and Sons Ltd
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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.

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Preface

TAUTOMERISM: INTRODUCTIN, HISTORY, AND RECENT DEVELOPMENTS IN EXPERIMENTAL AND THEORETICAL METHODS

The Definition and Scope of Tautomerism: Principles and Practicalities

Causes of Reversal in Tautomeric Form: Aromatic Resonance

Causes of Reversal in Tautomeric Form: Lone–Pair and Dipolar Repulsion

Causes of Reversal in Tautomeric Form: Selective Stabilization Through "Far" Intramolecular Hydrogen Bonding

Changes in Tautomeric Form Brought About by Electronegative Substituents

The Influence of Solvent on Tautomeric Form

Tautomeric Equilibrium: Historical Overview of an Analytical Problem

Short Historical Overview of Tautomerization Dynamics

Conclusions and Outlook

ABSORPTION UV–vis SPECTROSCOPY AND CHEMOMETRICS: FROM QUALITATIVE CONCLUSIONS TO QUANTITATIVE ANALYSIS

Introduction

Quantitative Analysis of Tautomeric Equilibria

Analysis of Real Tautomeric Systems

Concluding Remarks

STUDIES OF PHOTOINDUCED NH TAUTOMERISM BY STATIONARY AND TIME–RESOLVED FLUORESCENCE TECHNIQUES

Introduction

Photoinduced Proton/Hydrogen Atom Transfer

Fluorescence Techniques for Studying Tautomerism

Tautomerism in Bifunctional NH/N Azaaromatics

Ab initio and DFT Computational Methods

NH Tautomerism as a Tool in Biophysics

Concluding Remarks

FEMTOSECOND PUMP–PROBE SPECTROSCOPY OF PHOTOINDUCED TAUTOMERISM

Introduction

Ultrafast Pump–Probe Spectroscopy

Dynamics from Pump–Probe Spectroscopy

Reaction Mechanism

Reaction–Path–Specific Wavepacket Dynamics in Double ESIPT

Internal Conversion

Summary and Conclusions

NMR SPECTROSCOPY STUDY OF TAUTOMERISM IN SOLUTION AND IN THE SOLID STATE

Introduction

Methodologies of NMR Spectroscopy to Study Tautomerism

Types of Tautomerism Studied by NMR Spectroscopy

Conclusions and Outlook

ISOTOPE EFFECTS ON CHEMICAL SHIFTS AS A TOOL IN THE STUDY OF TAUTOMERIC EQUILIBRIA

Introduction

Experimental Requirements

Isotope Effects on Chemical Shifts

Secondary Equilibrium Isotope Effects on CS

Primary Isotope Effects

Solid State

Theoretical Calculations

Examples

Overview

TAUTOMER–SELECTIVE SPECTROSCOPY OF NUCLEOBASES, ISOLATED IN THE GAS PHASE

Introduction

Techniques

Guanine

Adenine

Cytosine

Uracil and Thymine

Base Pairs

Outlook

DIRECT EVIDENCE OF SOLID–STATE TAUTOMERISM BY DIFFRACTION METHODSD: ISOMERS, EQUILIBRIA, AND KINETICS

Application of X–Ray Diffraction to Study Tautomerism

Examples of X–Ray Diffraction Analysis of Proton Transfer

Other Diffraction Methods Used to Study Proton Transfer Reactions

DYNAMICS OF GROUND– AND EXCITED–STATE INTRAMOLECULAR PROTON TRANSFER REACTIONS

Introduction

Transition State Theory

Two Examples of Tautomerization

The Role of the Solvent

Solvent Friction and Solvent Dynamics

The Solvent Coordinate: Basics

Polarization Fluctuations

The Solvent Coordinate: An Application

Electronic Rearrangement

The Rug that Ties the (Classical) Room Together

Quantum and Classical

Quantum Decay

Coupling Quantum and Classical Motion: A Simple Example

Nonlinear Optics

Femtochemistry

Concluding Remarks

FORCE FIELD TREATMENT OF PROTON AND HYDROGEN TRANSFER IN MOLECULAR SYSTEMS

Introduction

Computational Approaches to Proton Transfer

Proton Transfer Reactions with MMPT

Applications of MMPT

Discussion and Outlook

THE SCOPE AND LIMITATIONS OF LSER IN THE STUDY OF TAUTOMER RATIO

Introduction

The Taft–Kamlet LSER Methodology

LSER Case Histories in the Field of Tautomerism

Overview

THE "BASICITY METHOD" FOR ESTIMATING TAUTOMER RATIO: A RADICAL RE–APPRAISAL

Introduction

Experimental Protocol

The Derivation of Correction Factors

Regularities Revealed by Correction Factors

Complicating Factors in the Use of the "Basicity Method"

Tautomeric Problems to Which the "Basicity Method" Is Inapplicable

Overview

QUANTUM CHEMICAL CALCULATION OF TAUTOMERIC EQUILIBRIA

Introduction

Computational Procedures

Solvent Effects

Applications of Quantum Chemical Methods to Tautomeric Equilibria

Concluding Remarks

Index

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Liudmil Antonov
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