Tricoordinated cyclic boron cations result from gas-phase ion/molecule reactions of dicoordinated borinium ions with neutral acetals and ketals and thiazolidine. The reaction, which proceeds via initial cationic binding to a heteroatom followed by a consecutive ring-opening and ring-reclosing process, resembles the Eberlin transacetalization of acylium ions (Eberlin, M. N.; Cooks, R. G. Org. Mass Spectrom. 1993, 28, 679). The cyclic structure of the tricoordinated boron cation is demonstrated by tandem mass spectrometry and further confirmed by comparison with authentic cyclic tricoordinated boron cations. The five-membered cyclic boron cations dissociate by ethylene oxide loss to thus reform the reactant-dicoordinated borinium ion; the six-membered boron cations fragment instead by ethylene loss. Consistent with the proposed mechanism, the ion/molecule reaction efficiency falls in the order CH(3)OB(+)C(2)H(5) > CH(3)OB(+)OCH(3) >> CH(3)B(+)CH(3); i.e., the higher the nucleophilicity of the borinium ion, the higher the reaction efficiency. A potential energy surface is calculated for the reaction of CH(3)OB(+)OCH(3) with 2-methyl-1,3-dioxolane, and the reaction is found to be 43.3 kcal/mol exothermic due to initial formation of a strong B-O bond. The analogous reactivity displayed by phosphonium ions is also investigated by both experiment and ab initio calculations. In contrast to the borinium ions, the phosphonium ions exhibit higher regioselectivity for sulfur compared to nitrogen and oxygen. Finally, the present findings indicate that the reaction exothermicity and the regioselectivity are controlled by both the Lewis acidity of the reactant cations and the leaving ability of the released neutrals in the rate-limiting nucleophilic-induced recyclization step.