The Encyclopedia of Mass Spectrometry - 1st Edition - ISBN: 9780080438467, 9780080913230

The Encyclopedia of Mass Spectrometry

1st Edition

Volume 4: Fundamentals of and Applications to Organic (and Organometallic) Compounds

Editors: Nico Nibbering
eBook ISBN: 9780080913230
Hardcover ISBN: 9780080438467
Imprint: Elsevier Science
Published Date: 8th December 2004
Page Count: 950
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Volume 4: Organic and Organometallic Compounds presents a cross section of applications in organic and organometallic chemistry in two parts. Chapters 1 to 6 are devoted to the fundamentals whereas chapters 7 and 8 cover applications to organic and organometallic compounds, either available as pure compounds or present in complex mixtures.

Chapter 1 describes the theory for organic mass spectrometry, building on and complementing material in Volume 1. The themes for Chapter 2 are the structures and properties of gas-phase ions of conventional, distonic, and non-covalent complexes. Chapter 3 covers methodology used in study of gas-phase ions. Chapters 4 and 5 turn to mechanisms of both unimolecular and bimolecular reactions of ions and include topics in stereochemistry and radical chemistry. Chapter 6 contains a number of articles on the formation and reactivity of metal ion complexes and organometallic cations and anions, drawing connections with molecular recognition, catalysis and organic synthesis.

Chapter 7 deals with the structure determination of organic compounds, including chiral compounds and natural products. In chapter 8 are contributions that provide illustrative examples of the determination of organic compounds present at low levels in complex samples that originate from various natural and biological sources. Included is an article on the determination of explosives.

Key Features

  • Cross section of the field of Organic and Organometallic MS
  • Covers fundamental Ion Chemistry as well as applications from simple to complicated systems
  • Suitable for new graduate students entering the field


Advanced Research Scientists; Mass Spectrometrists; Spectroscopists; Analytical Chemists; and those working in these fields

Table of Contents

Chapter 1. General Concepts. Thermochemical and Kinetic Factors Controlling Fragmentation. The Statistical Theory for Unimolecular Decay of Organic and Organometallic Ions. Appearance Energies. Potential Energy Surfaces. Kinetic Isotope Effects. Linear free energy correlations in mass spectrometry. Stevenson's Rule. Gas Phase Basicities, Experiment and Theory. Gas-phase acidities, Experiment and Theory. Metal Ion Affinities, Experiment and Theory.

Chapter 2. Structures and Properties of Gas-Phase Organic Ions. Radical-cations, overview. Alkanes, alkanes, and aromatic hydrocarbons. Alkylamine radical cations. Enol ions. Radical cations of saturated carboxylic acids, esters and amides. Structures and Properties of Gas-Phase Organic Ions: Sulfur (HS-, -S-, -SS-) Ions. Ion-molecule reactions of distionic radical cations. Theoretical models for ion-neutral complexes in unimolecular ion decompositions. Hydrogen-bridged cations. Even Electron Ions, Overview. Carbocations. Tropylium and related ions. Acylium ions. Oxonium Ions and Sulfur Analogs. Protonated Aromatics and Arenium Ions. Halonium and Halenium Ions. Ion Structures Produced in Gas Phase Radiolysis. Carbanions: Formation, Structure and Thermochemistry. H/D Exchange of Hydrocarbon Ions.

Chapter 3. Methods of Studying Gas-Phase Ions.
Structure and mechanism in organic ions. Use of potential energy surfaces to understand decomposition. Use of Wahrhaftig Plots to Understand Decompns. Pyrolysis mass spectrometry. Field Ionization Kinetics in Mass Spectrometry. Electron-Capture Dissociation. IRMPD. Photochemistry and Spectroscopy of Organic Ions. Radiolysis of Organic Compounds.

Chapter 4. Unimolecular Dissociations of Organic Ions. Molecular Hydrogen Elimination. Simple bond cleavage. Charge-remote fragmentation. Elimination Reactions. Cycloreversion Reactions. Hydrogen Rearrangements. McLafferty and Related Reactions. Hidden Hydrogen Rearrangements. Reactions that Reveal Stereochemistry. Functional Group Interactions. Negative Ion Mass Spectra of Underivatised. Peptides: An Aid to Sequence Determination. Mass spectrometric discrimination of acyclic stereoisomers via competing unimolecular decompositions. Fragmentations of Carbanions and Enolate Anions Directed from the Anionic Centre: An Aid to Structure Determination. Mass Spectrometric Fragmentations by Interaction of Ortho-Substituents of Aromatic Compounds.

Chapter 5. Reactions of Organic Molecules with Organic Ions. Organic Ion/Molecule Reactions, Overview. Additions to Multiple Bonds. Reactions of anions with carbonyl centres: C-C bond forming reactions. Riveros and Related Reactions. Cyclization and cycloaddition reactions. Stereoselective carbanion reactions. Radical Cation Mediated Aromatic Substitution Reactions. SN2 Reactions and Double-Well Potentials. Radical reactions as modeled by distonic ions. Radicals and Mass Spectrometry. Charge Transfer Fundamentals. Charge Transfer Applications. Proton Transfer Reactions Involving Multiply Charged Ions. Determinations of enantiomeric excess by ion/molecule reactions.

Chapter 6. Metal Ion Complexes: Formation and Reactivity. Metal Ion Complexes, Overview. Alkali Metals and Nucleic Acid Bases. Alkali Metals and Carbohydrates. Alkali metals and cyclic peptides. Alkaline Earths, Diketone/Metal Ion Complexes, Keto-Enol, Chelation. Organometallic Catalysis in the Gas Phase. Ion/molecule reactions of a selection of C5H5M+ ions. Transition Metal Oxide Cluster Anions and their Reactivity in the Gas Phase. Ion-Molecule Reactions as a Probe of Gas-Phase Structure of Metal Complexes. Gas-Phase Reactivity of Lanthanide Cations. Gas-Phase Reactions of Metal Ions with (Substituted) Benzenes. Remote Functionalization in the Gas Phase. Transition Metal Pi-Complexes, Stereochemical Effects. Activation of Aromatic Rings by Early Transition Metals in the Gas Phase. Photoexcitation Effects on Bimolecular Reactions of Metal Ion Complexes. Reactions of Metal Carbonyl Anions with Small Molecules. Reactions of metal carbonyl anions with small molecules. The Generation of Elusive Metal Complexes by Neutralization-Reionization Mass Spectrometry (NRMS). Heavy Main Group Element Containing Organic Compounds.

Chapter 7. Structure Determination of Organic Compounds. Structure Determination of Organic Compounds: Rules for Mass Spectra Interpretation: The Standard Interpretation Procedure. Unsaturated Compounds with Heteroatoms (Aldehydes, Ketones, Acids, Nitriles). Chiral Compounds. Alkaloids. Mass spectrometry of amino acids and small peptides. Organometallics (Early Transition Metals). H/D Exchange for Active H Counting in CI.

Chapter 8. Determination of Organic Compounds by Methods Using Mass Spectrometry Role of GC/MS in Petroleum Industry and Petrochemistry. Mass Spectrometry of Coal Liquids. Herbicides. Mass Spectrometric determination of analgesics and anesthetics and their metabolites. Mass Spectrometry of Antibiotics. Applying Mass Spectrometry to the Analysis of Flavors and Fragrances. Mass spectrometry in pheromone research Marine Toxins. Organic Materials in Forensic Science. Organic Materials in Geology. Organic Substances in Nutrition. Drugs of abuse in blood,urine. Emissions from combustion sources. Explosives.


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© Elsevier Science 2005
Elsevier Science
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About the Editor

Nico Nibbering

Affiliations and Expertise

Free University of Amsterdam


"I just received a copy of Volume 4 of the Encyclopedia of Mass Spectromtery: Fundamentals of and Applications to Organic (and Organometallic) Compounds. This may be the single greatest book published on mass spectrometry and undoubtedly will be used by a multitude of mass spectrometrists over the next many years to come." --David Sparkman, Consultant-At-Large, USA

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