The association of CH3+ with the three molecules C2N2, CH2CHCN, and HCCCN has been examined using ion cyclotron resonance (ICR) and selected ion flow tube (SIFT) techniques at room temperature. In each reaction, the mean lifetime of the complex (CH3 . N=C-R(+))* formed in the association has a major influence on the outcome of the reaction and the product channels that are observed using ICR and SIFT. Termolecular rate coefficients are reported for the association of CH3+ + C2N2 for the bath gases M = He, Ar, N-2, and C2N2. k(3) = 8.2 x 10(-24) cm(6) s(-1) (M = C2N2). In each system the association product channel occurs in competition with exothermic bimolecular channels. The complex lifetimes in all three systems are in the range 30-70 mu s. Very rapid ion-molecule association reactions have been observed in several systems of hydrocarbons and nitriles, and the implications for Titan ion chemistry are discussed briefly.