We report the synthesis and structural characterization of five-coordinate complexes of rhodium and iridium of the type [(eta(5)-C5Me5) M((NN)-N-boolean AND)](+) (3-M+), where (NN)-N-boolean AND represents the aminopyridinate ligand derived from 2-NH(Ph)-6-(Xyl)C5H3N (Xyl = 2,6-Me2C6H3). The two complexes were isolated as salts of the BArF anion (BArF = B[3,5-(CF3)(2)C6H3](4)). The M-N-amido bond of complexes 3-M+ readily activated CO, C2H4, and H-2. Thus, compounds 3-M+ reacted with CO under ambient conditions, but whereas for 3-Rh+, CO migratory insertion was fast, yielding a carbamoyl carbonyl species, 4-Rh+, the stronger Ir-N-amido bond of complex 3-Ir+ caused the reaction to stop at the CO coordination stage. In contrast, 3-Ir+ reacted reversibly with C2H4, forming adduct 5-Ir+, which subsequently rearranged irreversibly to [Ir] (H)(=C(Me)N(Ph)-) complex 6-Ir+, which contains an N-stabilized carbene ligand. Computational studies supported a migratory insertion mechanism, giving first a beta-stabilized linear alkyl unit, [Ir] CH2CH2N(Ph)-, followed by a multistep rearrangement that led to the final product 6-Ir+. Both beta- and alpha-H eliminations, as well as their microscopic reverse migratory insertion reactions, were implicated in the alkyl-to-hydride carbene reorganization. The analogous reaction of 3-Rh+ with C2H4 originated a complex mixture of products from which only a branched alkyl [Rh] C(H) (Me)N(Ph)- (5-Rh+) could be isolated, featuring a beta-agostic methyl interaction. Reactions of 3-M+ with H-2 promoted a catalytic isomerization of the Ap ligand from classical kappa(2)-N,N' binding to kappa-N plus eta(3)-pseudoallyl coordination mode.