Nitrenes and Nitrenium Ions

ISBN-13: 9780470390597 / Angielski / Twarda / 2013 / 598 str.

D. Falvey

Opis

Featuring contributions respected leaders in the field, Nitrene and Nitrenium Ions is the first comprehensive book to explore the role of reactive intermediate nitrene and nitrenium ions in chemistry and biochemistry. Covering a broad range of topics, including ultrafast studies, computational studies, behavior in aqueous solution, electronic structures, and reactions with aromatic compounds, this valuable resource will empower graduate students and researchers to better understand and expand their synthetic utility.

Spis treści

Preface to the Series vii

Introduction ix

Contributors xi

1 Ultrafast Time–Resolved Studies of the Photochemistry of Aryl Azides 1
Jin Wang, Gotard Burdzinski, and Matthew S. Platz

2 Theory and Computation in the Study of Nitrenes and their Excited–State Photoprecursors 33
Shubham Vyas, Arthur H. Winter, and Christopher M. Hadad

3 Nitrenium Ions and Related Species in Photoaffinity Labeling 77
R. Marshall Wilson and Valentyna Voskresenska

4 Aryl Nitrenium Ions in Aqueous Solution 117
Michael Novak and Yue–Ting Wang

5 Triplet Alkyl Nitrenes 167
Sivaramakrishnan Muthukrishnan, Ranaweera A. A. U. Ranaweera, and Anna D. Gudmundsdottir

6 Electronic Properties of Nitrenium Ions 191
Daniel E. Falvey

7 Time–Resolved Resonance Raman Spectroscopic Studies of Aryl Nitrenium Ions and their Chemical Reactions 217
David Lee Phillips

8 Matrix Studies on Aromatic and Heteroaromatic Nitrenes and their Rearrangements 273
Curt Wentrup

9 Nitreno Radicals 317
Dirk Grote and Wolfram Sander

10 Synthetic Applications of Nitrenium Ions 347
Duncan J. Wardrop and Edward G. Bowen

11 Fluorinated Aryl Nitrene Precursors 451
Elisa Leyva, Denisse de Loera, Socorro Leyva, and Rogelio Jimenez–Cata∼no

12 Properties of Carbonyl Nitrenes and Related Acyl Nitrenes 481
Nina P. Gritsan

Index 549

O autorze

DANIEL E. FALVEY, PhD, is Professor at the University of Maryland. His research focuses on reaction mechanisms and reactive intermediates, with an emphasis on the exploration of intermediates that play a role in biochemical processes. Dr. Falvey has been awarded the Merck Award and the Reynold C. Fuson Memorial Award in Chemistry. Acclaimed for his teaching abilities, he has received the Outstanding Teacher Award from the Center for Teaching Excellence.

ANNA D. GUDMUNDSDOTTIR, PhD, is Professor of Chemistry at the University of Cincinnati. Dr. Gudmundsdottir′s studies photo–removeable protecting groups, reactive intermediates, and polymer modification. Her research team elucidated the reactivity of triplet alkyl and vinyl nitrenes in solution and solid state using transient spectroscopy and matrix isolation. Among her many honors, Dr. Gudmundsdottir is a recipient of the NSF CAREER Award.

Blurb

Presents advanced experimental and theoretical methods to characterize nitrenes and nitrenium ions

Nitrenes and nitrenium ions are reactive intermediates with monovalent nitrogen atoms. These intermediates have diverse reactive and physical properties, depending on their structure and spin state. With contributions from leading international experts in nitrene chemistry, this book describes the most advanced computational, spectroscopic, and chemical methods for characterizing and working with these important reactive intermediates. Throughout the book, the authors identify a broad range of tested and proven methods to form nitrenes and nitrenium ions. Moreover, they explain how to take full advantage of their reactive properties to support a variety of applications.

Nitrenes and Nitrenium Ions begins with a brief overview and then explores current and emerging topics in the field such as:

• Exciting new findings stemming from advanced femtosecond and time–resolved vibrational spectroscopy studies that reveal unexpected complexities in the behavior of arylnitrene and nitrenium ions
• Dynamics and properties of nitrenes and nitrenium ions discovered using contemporary computational methods
• Behavior of nitrenes and nitrenium ions in biochemical and synthetic reactions
• Nitrenes and nitrenium ions with unusual structures or physical properties
• Role of nitrenes and nitrenium ions in biochemical processes that damage DNA

Each chapter, dedicated to a specific research topic, ends with references that provide a gateway to the original research studies and reviews in the field.

Nitrenes and Nitrenium Ions is recommended for students and researchers who want to improve their understanding of these important reactive intermediates and take full advantage of them in order to develop a variety of fine chemicals and pharmaceuticals.