Nmr in Organometallic Chemistry

by Pregosin, Paul S.

• ISBN13: 9783527330133
• ISBN10: 3527330135
• Edition: 1st
• Format: Paperback
• Copyright: 2012-05-21
• Publisher: Wiley-VCH

Summary

The first and ultimate guide for anyone working in transition organometallic chemistry and related fields, providing the background and practical guidance on how to efficiently work with routine research problems in NMR. The book adopts a problem-solving approach with many examples taken from recent literature to show readers how to interpret the data. Perfect for PhD students, postdocs and other newcomers in organometallic and inorganic chemistry, as well as for organic chemists involved in transition metal catalysis.

Author Biography

Paul S. Pregosin received his Ph. D. at the City University of New York. He then carried out postdoctoral research at Queen Mary College, University of London (1970 ? 1971), and at the University of Delaware (1971 ? 1973). In 1973, he moved to Swiss Federal Institute of Technology in Zurich, Switzerland, where he became Professor of Inorganic Chemistry in 1987. He has also received the Werner Prize
for his work on NMR-spectroscopic studies of transition metal complexes.

Table of Contents

PREFACE

INTRODUCTION

ROUTINE MEASURING AND RELAXATION
Getting Started
Relaxation

COSY AND HMQC 2-D SEQUENCES
Tactics
COSY
HMQC and HMBC

OVERHAUSER EFFECTS AND 2-D NOESY
Background
Assigning Signals via NOEs and General Applications
X,1H Overhauser Effects
2-D NOESY
HOESY
Metal Complexes and NOEs. ROESY vs NOESY

DIFFUSION CONSTANTS VIA NMR MEASUREMENTS

CHEMICAL SHIFTS
1HNMR
Introduction to Heavy Atom NMR
13C
15N NMR
19F NMR
31P NMR
Transition Metals

COUPLING CONSTANTS
Background
One-Bond Interactions
A Short 19F Excursion
Applications Involving 1J
1J(H,D) and Molecular Hydrogen Complexes
1J(C,H) in ?2-C-H M Complexes: Agostic Interactions
Remote Agostic Bonds
1J(Si,H) in ?2-Si-H M Complexes
Trans Influence and 1J
Two- and Three-Bond J-Values

DYNAMICS
Variable Temperature
Line Shape Analysis
Magnetization Transfer
Two-Dimensional NMR and Chemical Exchange

PREFACE TO THE PROBLEMS

ORGANOMETALLIC INTRODUCTION
Oxidative Addition
Migratory Insertion (or Intramolecular Nucleophilic Attack)
External Nucleophilic Attack
Beta-Hydrogen Elimination
Reductive Elimination
Synthesis of Transition Metal?Hydride Complexes
Synthesis of Transition Metal Alkyl Complexes
Synthesis of Transition Metal Carbonyl Complexes
Synthesis of Transition Metal Olefin Complexes
Synthesis of Transition Metal Carbene Complexes

NMR PROBLEMS
Three Sample Problems
NMR Problems

SOLUTIONS TO THE PROBLEMS AND COMMENTS