Metal Vapour Synthesis (MVS) can be defined as; "The use in synthesis of high temper­ ature gaseous species such as metal atoms by their reactions with themselves or other materials in a condensed phase. " This short book, covering the literature up to the middle of 1979, describes MVS in organic chemistry; i. e. the reactions of metal atoms with various, predominantly organic, substrates in the synthesis and reactivity studies of organic and organometallic compounds. In order to effectively describe all the underlying principles and to present a coesive picture of pertinent metal atom processes in condensed organic phases, some inorganic substrates such as rare gases, dinitrogen, dioxygen, dihalo­ gens, and inorganic halides have been included. For similar reasons, we have used, where relevent, information provided by the closely related technique of Matrix Isolation Spec­ troscopy (MIS). After an introductory chapter which gives the basis principles and includes a brief critique of the technique, the book is divided into three further chapters dealing respec­ tively with (a) experimental techniques, (b) behaviour of metal atoms in matrices, and (c) results of prep~rative experiments. While not being encyclopaedic the book describes or refers to all noteworthy areas if not in the deliberately short text in the many tables and figures.

Inhalt

1 The Basic Principles.- 1.1 Introduction.- 1.2 The Method.- 1.2.1 Metal Atom Source.- 1.2.2 The Reaction Site.- 1.2.3 Source of Coreactants.- 1.3 The Scope of the Technique.- 1.3.1 Synthesis of New Compounds.- 1.3.2 Improved Syntheses of Known Materials.- 1.3.3 A Quick Convenient Research Tool.- 2 Practical Aspects of Metal Vapour Synthesis.- 2.1 General Considerations.- 2.2 Pumping Systems.- 2.3 Vacuum Vessels.- 2.3.1 Static Vessels.- 2.3.2 Rotating Vessels.- 2.4 Reactant Inlet Systems.- 2.5 Vacuum Sealed Inlets for Electrical Supply.- 2.5.1 Low Tension.- 2.5.2 High Tension.- 2.6 Pressure Measurement.- 2.7 Vaporisation Sources.- 2.7.1 Resistance Heating.- 2.7.2 Electron Beam Heating.- 2.7.3 Laser Heating.- 2.7.4 Inductive Heating.- 2.7.5 Cathode Sputtering.- 2.7.6 Reactive and Activated Reactive Vaporisation.- 2.7.7 Ionised Cluster Beam Deposition.- 2.7.8 Electric Arc Heating.- 2.8 Vaporisation Sources for Matrix Isolation Spectroscopy.- 2.8.1 Foils and Wires.- 2.8.2 Knudsen Cells.- 2.8.3 Hollow-Cathode Sputtering Device.- 2.9 Leak Detection.- 2.10 General Experimental Procedures.- 2.10.1 Experiments with a Solid Matrix.- 2.10.2 Experiments in the Liquid Phase.- 2.10.3 Experiments in the Solid Phase.- 2.10.4 Experiments with Metal Slurries.- 2.10.5 Metal Aggregation and Catalysis.- 2.10.6 Cleaning.- 3 Properties of Metal Atoms and Interactions with Atoms and Molecules in Condensed Phases.- 3.1 Introduction.- 3.2 Metal Atoms in Matrices.- 3.2.1 Absorbtion Frequency Shifts in Matrix Isolated Metal Atom Spectra.- 3.2.2 Site Symmetry Effects.- 3.2.3 Reactions of Metal Atoms with Substrates.- 3.3 Metal-Metal Interactions: Aggregation.- 3.3.1 General Considerations.- 3.3.2 Dynamics of Metal Atom Aggregation.- 3.3.3 The Spectroscopic Characterisation of Metal Clusters.- 3.3.4 Nucleation and Free Energy of Small Clusters.- 3.3.5 Theoretical Considerations.- 3.4 Metal Atom Interactions in Synthetic Experiments.- 3.4.1 Vapour Zone.- 3.4.2 Cocondensation Zone.- 3.4.3 Rigid Matrix Zone or Period.- 3.4.4 Fluid Matrix Period.- 3.4.5 Solution Period.- 4 The Reactions of Metal Atoms.- 4.1 Types of Reaction.- 4.2 Carbon Monoxide.- 4.3 Carbon Monosulfide.- 4.4 Carbon Dioxide, Carbon Oxysulfide and Carbon Disulfide.- 4.5 Dinitrogen.- 4.6 Nitrogen Oxides.- 4.7 Phosphines and Phosphites.- 4.8 Isocyanides.- 4.9 Alkynes.- 4.10 Alkenes.- 4.11 Allyl.- 4.12 Alkadienes.- 4.12.1 Butadiene.- 4.12.2 Alkadienes with Active Hydrogens.- 4.12.3 Norbornadiene.- 4.13 Alkatrienes.- 4.13.1 Arenes.- 4.13.2 Cyeloheptatriene.- 4.14 Styrene.- 4.15 Alkatetraenes.- 4.16 Heterocycles.- 4.17 Boranes and Carboranes.- 4.18 Organic Halides.- 4.18.1 Reactions with Main Group Metal Atoms.- 4.18.2 Reactions with Transition Metal Atoms.- 4.19 Grignard Reagents.- 4.20 Inorganic Halides.- 4.21 Acids.- 4.22 Dioxygen.- 4.23 Dihalogens.- 4.24 Oxygen-Containing Organic Compounds.- 4.25 Sulfur-Containing Organic Compounds.- References.- Latest Developments in Metal Vapour Synthesis.