UID:
almafu_9959328770102883
Format:
1 online resource
ISBN:
9781118560877
,
1118560876
,
9781118560938
,
1118560930
,
9781118560853
,
111856085X
,
9781118560907
,
1118560906
,
9781299533899
,
1299533892
Series Statement:
Wiley series of reactive intermediates in chemistry and biology
Content:
"Nitrenes and Nitrenium ions are reactive intermediates with monovalent nitrogen atoms. These intermediates have diverse reactivity and physical properties, depending on their structure and spin state. The leading experts in nitrene chemistry have contributed to this book to highlight how spectroscopy and calculations have been used to characterize various nitrene intermediates. Emphasizes have also been placed on identifying the diverse methods to form these intermediates. Furthermore, the reactivity of nitrenes and nitrenium ions is discussed in details and how the reactivity can be used in various applications"--
Note:
Machine generated contents note: Preface Contributors Introduction Chapter 1. Ultrafast Studies of Azides and Nitrenes Jin Wang, Matthew S. Platz, The Ohio State University, Ohio, Gotard Burdzinski, Adam Mickiewicz University Poland Chapter 2. Computational Studies of Nitrenes and their Excited State Precursors Subham Vyas, Arthur H. Winter, Christopher M. Haddad, The Ohio State University, Ohio Chapter 3. Nitrenium Ions in Photoaffinity Labeling R. Marshall Wilson, Valentyna Voskresenska Bowling Green State University, Ohio Chapter 4. Nitrenium Ions in Aquoeous Solution Mike Novak, Yue-Ting Wang Miami University, Ohio Chapter 5 Triplet Alkylnitrenes Sivaramakrishnan Muthukrishnan, Ranaweera A.A.U. Ranaweera, Anna D. Gudmundsdottir, University of Cincinnati, Ohio Chapter 6. Electronic Structures of Nitrenium Ions Dan Falvey, University of Maryland, Maryland Chapter 7. Raman Studies of Nitrenium Ions David Lee Phillips, University of Hong Kong, Hong Kong Chapter 8. Matrix Studies of Heterocyclic Nitrenes Curt Wentrup University of Queensland, Australia Chapter 9. Dehydroaromatic Nitrenes Dirk Grote Wolfram Sander, Ruhr-Universitat Bochum, Germany Chapter 10. Synthetic Applications of Nitrenium Ions Duncan Wardrop, University of Illinois-Chicago, Illinois Chapter 11. Flourinated Nitrene Precursors Elisa Leyva, Denisse de Loera Socorro Leyva Jimenez-Catano, Univ. Autonoma San Luis Potosi, San Luis Potosi, Mexico Chapter 12. Acylnitrenes Nina Gritsan, Institute of Chemical Kinetics and Combustion Novosibirsk, Russia Index.
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Nitrenes and Nitrenium Ions -- Contents -- Preface to the Series -- Introduction -- Contributors -- 1 Ultrafast Time-Resolved Studies of the Photochemistry of Aryl Azides -- 1.1 Introduction -- 1.2 Aryl Azide Excited States and Nitrenes -- 1.2.1 Ultrafast UV-Vis Studies -- 1.2.2 Ultrafast IR Studies -- 1.3 Aryl Nitrenium Ions -- 1.3.1 p-Biphenylyl Nitrenium Cation -- 1.3.2 o-Biphenylyl Nitrenium Cation -- 1.3.3 1-Naphthyl Nitrenium Cation -- 1.3.4 2-Naphthyl Nitrenium Cation -- 1.3.5 Phenyl Nitrenium Cation -- 1.3.6 2-Fluorenyl Nitrenium Cation and the Influence of Solvent -- 1.4 Conclusions -- Acknowledgments -- References -- 2 Theory and Computation in the Study of Nitrenes and their Excited-State Photoprecursors -- 2.1 Introduction -- 2.2 Structural and Electronic Properties of Nitrenes -- 2.2.1 The Electronic Landscape of Nitrenes -- 2.2.2 Singlet Electronic States of Nitrenes -- 2.2.3 Ambiguity of Singlet State Nitrene Configuration Designations as "Open-Shell" or "Closed-Shell" -- 2.2.4 Singlet-Triplet Gap of Nitrenes -- 2.2.5 Substituent Effects on Singlet Nitrene Configuration -- 2.2.6 Electronic Structure of Carbonylnitrenes -- 2.2.7 Comparison of the Molecular Structure Between Singlet and Triplet Phenylnitrene -- 2.2.8 Choice of Computational Method for Modeling Nitrenes -- 2.3 The Central Role of the Singlet Nitrene -- 2.3.1 Structural and Electronic Influences on the Rate of Nitrene Intersystem Crossing -- 2.3.2 Energy Barriers and Thermodynamics of Diazirine Formation -- 2.3.3 Protonation of Nitrenes to Yield Nitrenium Ions -- 2.3.4 Extending Singlet Nitrene Lifetime Through Inhibition of Alternative Decay Channels -- 2.3.5 Possibility of Excited State Nitrene Reactions-Exceptions to Kasha's Rule? -- 2.4 Precursors to the Nitrene -- 2.4.1 Different Precursors to Nitrene Formation -- 2.4.2 Geometry and Electronic Structure of Azides.
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2.5 Structure and Photochemistry of Homo-Azides -- 2.5.1 Alkyl Azides -- 2.5.2 Vinyl Azides -- 2.5.3 Aryl Azides -- 2.6 Structure and Photochemistry of Hetero-Azides -- 2.6.1 Carbonyl Azides -- 2.6.2 Phosphyl Azides -- 2.6.3 Other Azides -- 2.7 Unanswered Questions and Calculations to be Performed -- Acknowledgments -- References -- 3 Nitrenium Ions and Related Species in Photoaffinity Labeling -- 3.1 Introduction -- 3.2 Reactions of Nitrenium Ions with Biomolecules -- 3.2.1 Properties of Aryl Azides that Serve as Nitrenium Ion Precursors -- 3.3 Applications of Aryl Nitrenium Ions in Photoaffinity Labeling -- 3.3.1 4-Azido-2-nitrophenyl Amines -- 3.4 General Considerations -- 3.4.1 Purine Azides -- 3.5 Conclusions -- References -- 4 Aryl Nitrenium Ions in Aqueous Solution -- 4.1 Introduction -- 4.2 The Early Years (1894-1990) -- 4.3 Aryl Nitrenium Ions About 1990-2010 -- 4.3.1 Lifetimes of Nitrenium Ions -- 4.3.2 Acid-Base Chemistry -- 4.3.3 Heterocyclic Nitrenium Ions -- 4.3.4 Reactions with p-Nucleophiles -- 4.4 Future Prospects -- Acknowledgments -- References -- 5 Triplet Alkyl Nitrenes -- 5.1 Introduction -- 5.2 Direct Photolysis and Thermal Activation of Azidoalkanes -- 5.3 Direct Photolysis and Thermolysis of Geminal Diazidoalkanes -- 5.4 Intermolecular Triplet-Sensitized Photolysis of Azidoalkanes -- 5.5 Intramolecular Triplet-Sensitized Photolysis of Azidoalkanes -- 5.5.1 Characterization of Triplet Alkyl Nitrenes in Solution -- 5.5.2 Solution Reactivity of Triplet Alkyl Nitrene -- 5.5.3 Hydrogen Atom Abstraction by Triplet Alkyl Nitrenes -- 5.5.4 Oxygen Trapping of Triplet Alkyl Nitrenes -- 5.5.5 Photoreactions that Compete with Intramolecular Energy Transfer in Alkyl Azides -- 5.6 Conclusions -- Acknowledgments -- References -- 6 Electronic Properties of Nitrenium Ions -- 6.1 Introduction -- 6.2 NH2+ and other Triatomic Nitrenium Ions.
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6.3 Alkyl- and Dialkyl-Nitrenium Ions -- 6.4 Vinyl-, Acyl-, and Alkoxy-Nitrenium Ions -- 6.5 Aryl Nitrenium Ions -- 6.6 Alkylaryl Nitrenium Ions -- 6.7 Diaryl Nitrenium Ions -- 6.8 Heteroaryl Nitrenium Ions -- 6.9 Conclusions -- References -- 7 Time-Resolved Resonance Raman Spectroscopic Studies of Aryl Nitrenium Ions and their Chemical Reactions -- 7.1 Introduction -- 7.2 Experimental and Computational Methods -- 7.2.1 Nanosecond Time-Resolved Resonance Raman (TR3) -- 7.2.2 Ultrafast Time-Resolved Resonance Raman (TR3) Spectroscopy -- 7.2.3 Density Functional Theory Calculations -- 7.3 Time-Resolved Resonance Raman (TR3) Spectroscopy of Aryl Nitrenium Ions -- 7.3.1 Formation of Aryl Nitrenium Ions in Aqueous Solutions -- 7.3.2 TR3 Spectroscopy of Para-Phenyl-Substituted Phenyl Nitrenium Ions -- 7.3.3 TR3 Spectroscopy of Alkoxy-Substituted Phenyl Nitrenium Ions -- 7.3.4 TR3 Spectroscopy of Acetamido-Substituted Phenyl Nitrenium Ions -- 7.4 Time-Resolved Resonance Raman (TR3) Spectroscopy to Study Selected Chemical Reactions of Aryl Nitrenium Ions -- 7.4.1 Aryl Nitrenium Ion Reactions with Aryl Azides -- 7.4.2 Aryl Nitrenium Ion Reactions with Guanine Derivatives -- 7.5 Conclusions and Outlook -- Acknowledgments -- References -- 8 Matrix Studies on Aromatic and Heteroaromatic Nitrenes and their Rearrangements -- 8.1 Introduction -- 8.2 Ring Expansion -- 8.2.1 Azirenes -- 8.2.2 Bond-Switch Cumulenes (Cyclic Nitrile Ylides) -- 8.3 Ring Contraction -- 8.4 Ring Opening -- 8.4.1 Type I Ring Opening to Nitrile Ylides -- 8.4.2 Type II Ring Opening to Nitrenes or Diradicals -- 8.5 Conclusions and Outlook -- Acknowledgments -- References -- 9 Nitreno Radicals -- 9.1 Introduction -- 9.2 Theory -- 9.3 EPR Spectroscopy on Iodophenyl Nitrenes -- 9.4 Nitrene Rearrangement as Competition to The Formation of Nitreno Radicals.
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9.5 Matrix Isolation and Spectroscopic Characterization of Nitreno Radicals -- 9.5.1 Phenyl Nitrene-4-yl -- 9.5.2 Phenyl Nitrene-2-yl -- Acknowledgments -- References -- 10 Synthetic Applications of Nitrenium Ions -- 10.1 Introduction -- 10.2 Electronic Structure of Nitrenium Ions -- 10.3 General Reactivity of Nitrenium Ions -- 10.3.1 Parent Nitrenium Ion -- 10.3.2 Alkyl Nitrenium Ions -- 10.3.3 Aryl Nitrenium Ions -- 10.3.4 Alkylaryl Nitrenium Ions -- 10.3.5 Heteroatom-Stabilized Nitrenium Ions -- 10.4 Parent Nitrenium Ion -- 10.5 Alkyl Nitrenium Ions -- 10.5.1 Early Studies and Proof of Existence -- 10.5.2 Cyclization of Unsaturated N-Chloramines (The Nitrenium Ion Question) -- 10.5.3 Ring Expansion and Contraction of Alkyl Nitrenium Ions (or Equivalents) -- 10.6 Aryl Nitrenium Ions -- 10.6.1 Early Studies: Bamberger Rearrangement and Proof of Existence -- 10.6.2 Generation from Aryl Azides and Cyclization -- 10.6.3 Cyclization to Carbazoles, Indoles, and Related N-Heterocycles -- 10.7 Heteroatom-Stabilized Acyl Nitrenium Ions -- 10.7.1 Generation and Intramolecular Aromatic Substitution -- 10.7.2 Application of N-Acyl Nitrenium Ion Annulation to Target-Directed Synthesis -- 10.7.3 Application of N-Acyl Nitrenium Ion Spirocyclization to Target-Directed Synthesis -- 10.8 Intermolecular Alkene Addition of Stabilized Nitrenium Ions -- 10.8.1 Alkene Addition of N-Stabilized Nitrenium Ions -- 10.8.2 Alkene Addition of O-Stabilized and Aryl Nitrenium Ions -- 10.9 Intramolecular Alkene Addition of Stabilized Nitrenium Ions -- 10.10 Conclusions and Outlook -- Acknowledgments -- References -- 11 Fluorinated Aryl Nitrene Precursors -- 11.1 Introduction -- 11.2 Photochemistry of Phenyl Azide: A General Mechanism -- 11.3 Photochemistry of Fluorinated Phenyl Azides in Different Solvents -- 11.4 Photochemistry of Fluorinated Phenyl Azides in Amines.
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11.4.1 Reactions in Diethylamine -- 11.4.2 Reactions in Aniline -- 11.5 Oxidation of Fluoroanilines -- 11.6 Novel Fluoro Aryl Nitrene Precursors -- 11.6.1 Fluorinated 2-Nitrophenyl Azides and 2-Nitroanilines -- 11.6.2 7-Azido-1-ethyl-6,8-difluoroquinolone-3-carboxylate -- 11.7 Photoaffinity Labeling and Bifunctional Photochemical Probes -- 11.8 Conclusions and Outlook -- Acknowledgments -- References -- 12 Properties of Carbonyl Nitrenes and Related Acyl Nitrenes -- 12.1 Introduction -- 12.2 Generation and Properties of Carbonyl Nitrenes -- 12.3 Generation and Properties of Nitrene Esters -- 12.4 Generation and Properties of Sulfonyl Nitrenes -- 12.5 Generation and Properties of Phosphinyl- and Phosphoryl Nitrenes -- 12.5.1 Phosphinyl Azides and Nitrenes -- 12.5.2 Phosphoryl Azides and Nitrenes -- 12.6 Conclusions -- References -- Index.
Additional Edition:
Print version: Nitrenes and nitrenium ions. Hoboken, NJ : Wiley, 2013 ISBN 9780470390597
Language:
English
Keywords:
Electronic books.
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Electronic books.
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Electronic books.
URL:
https://onlinelibrary.wiley.com/doi/book/10.1002/9781118560907
URL:
https://onlinelibrary.wiley.com/doi/book/10.1002/9781118560907
URL:
https://onlinelibrary.wiley.com/doi/book/10.1002/9781118560907
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