Treatment of [Ir(bpa)(cod)](+) complex [1](+) with a strong base (e.g., tBuO(-)) led to unexpected double deprotonation to form the anionic [Ir(bpa-2H)(cod)](-) species [3](-), via the mono-deprotonated neutral amido complex [Ir(bpa-H)(cod)] as an isolable intermediate. A certain degree of aromaticity of the obtained metal-chelate ring may explain the favourable double deprotonation. The rhodium analogue [4](-) was prepared in situ. The new species [M(bpa-2H)(cod)](-) (M = Rh, Ir) are best described as two-electron reduced analogues of the cationic imine complexes [M(I)(cod)(Py-CH(2)-N=CH-Py)](+). One-electron oxidation of [3](-) and [4](-) produced the ligand radical complexes [3](*) and [4](*). Oxygenation of [3](-) with O(2) gave the neutral carboxamido complex [Ir(cod)(py-CH(2)-N-CO-py)] via the ligand radical complex [3](*) as a detectable intermediate.