(IP)2GaIII Complexes Facilitate Net Two-Electron Redox Transformations (IP = α‑Iminopyridine)

Reaction of M+[(IP2‑)2Ga]− (IP = iminopyridine, M = Bu4N, 1a; (DME)3Na, 1b) with pyridine N-oxide affords two-electron-oxidized (IP–)2Ga­(OH) (2) in reactions where the product outcome is independent of the cation identity, M+. In a second example of net two-electron chemistry, outer sphere oxidation of M+[(IP2‑)2Ga]− using either 1 or 2 equiv of the one-electron oxidant ferrocenium afforded [(IP–)2Ga]+ (3) in either 44 or 87% yield, respectively. Reaction with 1 equiv of TEMPO, a one-electron oxidant, afforded the two-electron-oxidized product (IP–)2Ga­(TEMPO) (4). Reduction of 2IP by 3Na and subsequent reaction with GaCl3 yielded a 1:1 mixture of (IP–)2GaCl and 1. Most remarkably, all of these reactions are overall two-electron processes and only the (IP–)2GaX and [(IP2‑)2Ga]− oxidation states are thermodynamically accessible to us. Analogous aluminum chemistry previously afforded either one-electron or two-electron reactions and mixed-valent states. The thermodynamic accessibility of the mixed-valent states of (IP2‑)­(IP–)­E, where E = Al or Ga, can be compared using cyclic voltammetry measurements. These measurements indicated that the mixed-valent state [(IP2‑)­(IP–)­Ga]+ is not significantly stabilized with respect to disproportionation on the time scale of the electrochemistry experiment. The electrochemically observed differences in thermodynamic stability of the mixed-valent state [(IP2‑)­(IP–)­E]+ can be rationalized by the observation that the dihedral angle between the ligand planes containing the π-system of IP is roughly 5° larger in all gallium complexes compared with aluminum analogs. Presumably, a larger dihedral angle provides weaker electronic coupling between the π-systems of IP via the E–X σ* orbital. Alternatively, the observed difference may be a result of the “inert pair effect”: a contracted Ga component in the E–X σ* orbital would also afford weaker electronic coupling.