A combined experimental and DFT study of the reactions of the titanium imido methyl cation [Ti((NBu)-Bu-t)(Me-3[9]aneN(3))Me](+) (4(+)) with AlMe3 and ZnMe2 is described. Reaction of 4(+) with AlMe3 gave [Ti((NBu)-Bu-t)(Me-3[9]aneN(3))(mu-Me)(2)AlMe2](+) (7(+)), the first structurally characterized AlMe3 adduct of a transition metal alkyl cation and a model for the presumed resting state in MAO-activated olefin polymerizations. Reaction of 4(+) with ZnMe2 also gave a methyl-bridged heterobinuclear species, namely [Ti(mu-(NBu)-Bu-t)(Me-3[9]aneN(3))(mu-Me) 2ZnMe](+) (8(+)), the first directly observed ZnMe2 adduct of a transition metal alkyl cation. At room temperature, all three metal-bound methyls of 8(+) underwent rapid exchange with those of free ZnMe2, whereas at 233 K only the terminal Zn-Me group exchanged significantly. Addition of AlMe3 to 8(+) quantitatively formed 7(+) and ZnMe2. Reaction of 4(+) with Cp2ZrMe2 gave [Ti((NBu)-Bu-t){Me-2(mu-CH2)[9]aneN(3)}(mu-CH2)ZrCp2]+ (10(+)) via a highly selective double C-H bond activation reaction in which both alkyl groups of Cp2ZrMe2 were lost. DFT calculations on models of 7(+) confirmed the approximately square-based pyramidal geometries for the bridging methyl groups. Calculations on 8+ found that the formation of the Ti(mu-Me)(2)Zn moiety is assisted by an N-imide -> Zn dative bond. DFT calculations for the sterically less encumbered methyl cation [Ti(NMe)(H-3[9]aneN(3))Me](+) found strong thermodynamic preferences for adducts featuring N-imide -> M (M = Al or Zn) interactions. This offers insight into recently observed structure-productivity trends in MAO-activated imido-based polymerization catalysts. Calculations on the metallocenium adducts [Cp2Ti(mu-Me)(2)AlMe2](+) and [Cp2Ti(mu-Me)(2)ZnMe](+) are described, each showing alpha-agostic interactions for the bridging methyl groups. For these systems and the imido ones, the coordination of AlMe3 to the corresponding monomethyl cation is ca. 30 kJ mol(-1) more favorable than for ZnMe2.