Gas Phase Inorganic Chemistry

1 Reactions of Atomic Metal Ions with H2, CH2, and C2H6: Electronic Requirements for H—H, C—H, and C—C Bond Activation.- 1. Introduction.- 1.1. Relation between Gas Phase and Condensed Phase.- 1.2. Electronic Requirements for Alkane Activation.- 1.3. State-Specific Chemistry.- 2. Ior Beam Techniques.- 2.1. Ion Sources.- 2.2. Experimental Considerations.- 2.3. Energy Behavior of Ion-Molecule Reactions.- 2.4. Comparison to ICR (FTMS) Techniques.- 3. Thermochemistry.- 3.1. From Endothermicities to Bond Energies.- 3.2. Ionic Metal Hydrides.- 3.3. Ionic Metal Methyls.- 3.4. Ionic MR2: R=H, CH3.- 3.5. Neutral Metal Methyls.- 3.6. Ionic Metal Methylidenes and Methylidynes.- 4. Reactions with Dihydrogen.- 4.1. Molecular Orbital Considerations.- 4.2. Spin Considerations.- 4.3. Periodic Trends in Reactivity.- 5. Reactions with Methane.- 5.1. Sc+ + CH4.- 5.2. Reaction Mechanism.- 5.3. Ti+, V+ + CH4.- 5.4. Cr+ + CH4.- 5.5. Fe+ + CH4.- 6. Reactions with Ethane.- 6.1. V+ + C2H6.- 6.2. Sc+ + C2H6.- 6.3. Fe+ + C2H6.- 6.4. Fe+ + C3H8.- 6.5. Zn+ + C2H6.- 7. Summary.- 7.1. Thermochemistry.- 7.2. Reactions with Dihydrogen.- 7.3. Reactions with Methane.- 7.4. Reactions with Ethane.- 7.5. Outlook.- References.- 2 Nucleophilic Addition Reactions of Negative Ions with Organometallic Complexes in the Gas Phase.- 1. Introduction.- 1.1. Nucleophilic Addition in Organometallic Chemistry.- 1.2. Previous Gas Phase Studies.- 2. The Flowing Afterglow Method.- 3. Mononuclear Transition Metal Carbonyls.- 3.1. Fe(CO)5.- 3.2. Group 5 and Group 6 Hexacarbonyls, M(CO)6 (M = V, Cr, Mo, W).- 3.3. Reactions with Partially Solvated Nucleophiles.- 4. Transition Metal Arene, Cyclopentadienyl, and Diene Complexes.- 4.1. (?6-C6H6)Cr(CO)3.- 4.2. (?5-C5H5)Mn(CO)3.- 4.3. Isomeric (C4H6)Fe(CO)3 Complexes.- 5. Catalysis Intermediates.- 5.1. Hydroxycarbonyl Complexes and the Homogeneously Catalyzed Water-Gas Shift Reaction.- 5.2. Hydride Transfer Reactions: Thermochemistry for Transition Metal Formyl Ions.- 6. Concluding Remarks.- References.- 3 Reactions in Ionized Metal Carbonyls: Clustering and Oxidative Addition.- 1. Mass Spectrometry of Metal Carbonyls.- 1.1. Binary Metal Carbonyls.- 1.2. Other Metal Carbonyls.- 1.3. Electronically Excited Fragment Ions.- 1.4. Negative Ion Mass Spectra.- 1.5. Thermochemistry of Fragment Ions.- 2. Clustering Reactions of Metal Carbonyl Ions with Metal Carbonyls.- 2.1. Early Results.- 2.2 Structure-Reactivity Relations in Clustering Reactions: Multiple Bonds in Iron Carbonyl Clusters.- 2.3. Structure-Reactivity Relations in Group 7 Metal Carbonyl Clusters: Large Polyhedral Structures.- 3. Ligand Substitution Reactions.- 4. Oxidative Addition Reactions of Atomic Transition Metal Ions.- 4.1. Reactions with Alkyl Halides and Alcohols.- 4.2. Reactions with Aryl Halides.- 4.3. Reactions with Alkanes.- 4.4. The Effect of Oxidation State: Reactions of Fe+, FeI+, and FeI2+.- 4.5. Reactions of Fe+ with Cycloalkanes: Transition State Geometries.- 5. Reactions of Polynuclear Metal Carbonyl Ions with Alkanes ..- 5.1. Reaction of Diatomic Metal Carbonyl Ions.- 5.2. Reactions of Rhenium Carbonyl Cluster Ions with Cycloalkanes.- References.- 4 Structure-Reactivity Relationships for Ionic Transition Metal Carbonyl Cluster Fragments.- 1. Electron Deficiency Model.- 2. Cluster Valence Molecular Orbital Model.- 3. Bonding of Fe(CO)x in Heterometallic Ionic Cluster Fragments.- 4. Metal-Metal and Metal-Ligand Binding Energies in Ionic Cluster Fragments of Transition Metal Carbonyls.- References.- 5 Metal and Semiconductor Cluster Ions.- 1. Introduction.- 2. Methods for Generating Cluster Ions.- 3. Methods for Studying Cluster Ions.- 4. Carbon Cluster Ions.- 5. Silicon Cluster Ions.- 6. Aluminum Cluster Ions.- 7. Transition Metal Cluster Ions.- 8. Concluding Discussion.- References.- 6 Atomic Clusters in the Gas Phase.- 1. Atomic Cluster Properties and Their Size Dependence.- 1.1. Interest in Atomic Clusters.- 1.2. N-Specific Properties.- 1.3. Theoretical Guidelines.- 2. Controlled Preparation (Synthesis) of Atomic Clusters.- 2.1. Requirements for Property Measurement.- 2.2. The Existing Methods.- 2.3. Comparison among Methods.- 3. The Basic Experimental Measurements.- 3.1. N-Specific Detection of Measured AN Properties.- 3.2. Natural Abundances and Cluster Growth Rates.- 3.3. The Ionization Potential and Electron Affinity.- 3.4. Electric and Magnetic Moments.- 3.5. Optical Spectroscopy.- 3.6. Photoelectron Spectroscopy (PES).- 3.7. Chemical Flow Reactors and Ion-Molecule Reactors.- 4. Review of Results.- 4.1. Main-Group Metals (Groups 1, 2, and 13).- 4.2. Noble Metal Clusters (Groups 11 and 12).- 4.3. Clusters of Transition Metal Atoms.- 4.4. Clusters of Groups 14 and 15 Elements.- 4.5. Rare-Gas Clusters.- 5. Prospectus: Outstanding Questions.- 5.1. Where Are the Isomers?.- 5.2. The Energetics of Chemical Reactions.- 5.3. Back to the Support.- References.- 7 Time-Resolved Kinetics of Organometallic Reactions in the Gas Phase by Transient Infrared Absorption Spectrometry.- 1. Introduction.- 2. Methods for the Detection and Infrared Spectral Characterization of Organometallic Intermediates in the Gas Phase.- 2.1. Pulsed UV Photolysis Sources.- 2.2. Infrared Sources.- 2.3. Infrared Detectors and Signal Processing Electronics.- 2.4. Experimental Setup for Gas Phase Transient Infrared Absorption Using an Incoherent Source.- 3. Review of Recent Progress in Gas Phase Organometallic Transient Infrared Absorption Spectroscopy.- 3.1. Fe(CO)5.- 3.2. Fe(CO)4(C2H4).- 3.3. Fe(CO)3(C2H4)2.- 3.4. Mn2(CO)10.- 3.5. Co(CO)3NO.- 3.6. Cr(CO)6.- 4. Time-Resolved Infrared Absorption Spectroscopy as a Probe of Dissociative CO-for-C2H4 Substitution in Cr(CO)4(C2H4)2.- 4.1. Background.- 4.2. Results and Discussion.- References.- 8 Characterization of Metal Complex Positive Ions in the Gas Phase by Photoelectron Spectroscopy.- 1. Introduction.- 2. Structural Information on Metal Positive Ions with Small Molecules in the Gas Phase.- 2.1. Background.- 2.2. Vibrational Fine Structure and Bond Distances in Metal Carbonyls.- 2.3. Jahn-Teller Effects and Angular Distortions in Metal Complex Positive Ions.- 3. Electron Distribution and Bonding in the Positive Ion.- 4. Ionization Energy-Bond Energy Relationships.- 4.1. Fundamental Relationships.- 4.2. Mn(CO)5 Bound to H, CH3, and Mn(CO)5.- 4.3. Electronic Factors of Carbon-Hydrogen Bond Activation.- References.- 9 Chemistry and Photochemistry of Bare Metal Cluster Ions in the Gas Phase.- 1. Introduction.- 2. Bimolecular Reactions of Metal Cluster Ions.- 2.1. Dissociative Chemisorption.- 2.2. Reactions with Organic Compounds.- 2.3. Oxide Chemistry.- 3. Unimolecular Reactions of Metal Cluster Ions.- 3.1. Photodissociation.- 3.2. Collision-Induced Dissociation and Unimolecular Dissociation.- 3.3. Multiply Charged Clusters.- 4. Conclusion.- References.- 10 Photodissociation of Metal-Containing Gas Phase Ions.- 1. Introduction.- 2. Experimental Methods.- 2.1. Ion Traps.- 2.2. Ion Beams.- 2.3. Clusters.- 3. Spectroscopy.- 3.1. What Color Are the Ions?.- 3.2. Organometallic Ions with Reasonably Complete Ligand Shells.- 3.3. Organometallic Ions with Major Coordinative Unsaturation.- 3.4. Diatomic Ions.- 3.5. Cluster Ions.- 4. Dissociation Products.- 4.1. What Do the Fragments Tell Us?.- 4.2. Ion Structures.- 4.3. Thermochemistry and Bond Strengths.- 4.4. Cluster Ions.- 5. Mechanistic Aspects.- 5.1. Probing the Details of the Photodissociation Process.- 5.2. Competitive Fragmentation.- 5.3. Infrared Laser Photochemistry.- 5.4. Angular Dependence.- References.- 11 Photodissociation of Gas Phase Metal Clusters.- 1. Introduction.- 2. Techniques.- 2.1. Detection of Organometallic Photoproducts by Chemical Trapping.- 2.2. Detection of Organometallic Photoproducts by Ionization Techniques.- 2.3. Detection of Organometallic Photoproducts by Spectroscopic Techniques.- 3. Examples.- 3.1. The Photofragmentation of Group 6 Complexes.- 3.2. The Photofragmentation of Group 7 Complexes.- 3.3. The Photochemistry of Group 8 Complexes.- 4. Conclusions.- References.- 12 Tandem Mass Spectrometry and High-Energy Collisional Activation for Studies of Metal Ion-Molecule Reactions.- 1. Introduction.- 2. Review of Tandem Instruments.- 2.1. Sector Instruments.- 2.2. Triple Quadrupoles.- 2.3. Hybrid Instruments.- 2.4. Fourier Transform Instruments.- 2.5. Collision Energy Considerations.- 2.6. Energy-Resolved Mass Spectrometry.- 3. Applications of MS/MS in Metal Ion Chemistry.- 3.1. Ion Beam Studies.- 3.2. Triple-Quadrupole Studies.- 3.3. Flowing Afterglow Studies.- 3.4. High-Energy Collisional Activation.- 3.5. Metastable Ion Studies.- 4. Conclusions.- References.