Abstract
Both positive and negative ion-molecule reactions of alkyl nitrites have been examined using the techniques of ion cyclotron resonance spectroscopy. In the case of positive ion-molecule reactions a variety of NO + transfer and hydride abstraction reactions dominate the ion chemistry. In all of the nitrites reaction sequences lead to the production of relatively stable nitrito alkyl cations. The negative ion-molecule reactions are characterized by NO 2 - production by nucleophilic displacement reactions and enolate formation via proton transfer and loss of NO. The proton affinities of each of the nitrites studied have been determined and compared to the gas phase basicities of the corresponding alcohols.
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