Nucleophilic Reactivity in Gas-Phase Anion—Molecule Reactions

Three different topics of nucleophilic anions reacting with neutral molecules are discussed. (1) O2·- is established intrinsically and kinetically as a super nucleophile in SN2 reactions with CH3X molecules. (2) The intrinsic reactivity scale of nucleophilic additions to carbonyl centers is developed by using C6H5N·- as the nucleophile and can be extended with (C6H5)2C·-. (3) The phosphoryl anion (CH3O)2PO- is shown to be a poor nucleophile in SN2 reactions with CH3X molecules but reacts rapidly with ICF3 and BrCF3 by initial electron transfer; mainly (CH3O)(X)P2- negative ions result.