Reactions with Other Addenda

Compounds of the Transition Elements 10.3.5. Reactions at a Group VilA Metal Center 10.3.5.4. Reactions with Other Addenda... 

Contents Introduction and Principles. - The Reaction of Dichlorocarbene With Olefins. - Reactions of Dichlorocarbene With Non-Olefinic Substrates. -Dibromocarbene and Other Carbenes. - Synthesis of Ethers. - Synthesis of Esters. - Reactions of Cyanide Ion. - Reactions of Superoxide Ions. - Reactions of Other Nucleophiles. - Alkylation Reactions. - Oxidation Reactions. - Reduction Techniques. - Preparation and Reactions of Sulfur Containing Substrates. -Ylids. - Altered Reactivity. - Addendum Recent Developments in Phase Transfer Catalysis. 

Equations 56 and 57 apply to monomolecular reactions in the gas phase at the low pressure limit where the rate determining step is the activating collision. On the other hand, at the high pressure limit the theory of RRK predicts (see, e.g.. Ref. 986) = Eo (see footnote, p. 245). This explains the experimentally observed decrease of Ea with decreasing pressure. The decrease of Ea with temperature at the low pressure limit, predicted by Eq. 57, is less pronounced, and is more difficult to observe (see Addendum). 

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