Redox active ligands are shown to facilitate a variety of group transfer reactions at redox inert aluminum(III). Disulfides can be used as a two-electron group transfer reagent, and we show that (IP-)(2)AlSR can be formed by reaction of [(THF)(6)Na][(IP2-)(2)Al] (1c) with disulfides RSSR (where X = C(S)NMe2, 4; SMe, 5). In a more general redox route to substitution of aluminum bis(iminopyridine) complexes, we report zinc(II) salts as a group transfer reagent. Reaction of [((IP2-)-I-R)(2)Al](-) (R = H, 1c; Me, 1d) with ZnX2 affords ((IP-)-I-R)(2)AlX (where IP = iminopyridine, R = H, and X = Cl, 2; CCPh, 6; N-3, 7; SPh, 8; or R = Me and X = NHPh, 9). Single crystal Xray diffraction analysis of the complexes reveal that each of the five coordinate complexes reported here has a trigonal bipyramidal geometry with tau = 0.668 - 0.858. We observed a correlation between the greatest deviations from ideal trigonal bipyramidal symmetry (lowest tau values), the bond lengths consistent with smallest degree of ligand reduction, and the least polarizable X ligand in (IP-)(2)AlX. Complex 4 is six-coordinate and is best described as distorted octahedral. Variable temperature magnetic susceptibility measurements indicate that each of the complexes 3-9 has a biradical electronic structure similar to previously reported 2. Magnetic exchange coupling constants in the range J = -94 to -212 cm(-1) were fit to the data for 2-9 to describe the energy of antiferromagnetic interaction between ligand radicals assuming a spin Hamiltonian of the form (H) over cap = -2J (S) over cap (L(1))center dot(S) over cap (L(2)). The strongest coupling occurs when the angle between the ligand planes is smallest, presumably to afford good overlap with the Al-X sigma* orbital. Electrochemical properties of the complexes were probed using cyclic voltammetry and each of 3-9 displayed a reversible two-electron reduction and two quasi-reversible one-electron oxidation processes. The energy of the ligand based redox processes for 2-9 differ by about 150 mV over all complexes and show a correlation with the degree of IP- reduction observed crystallographically; more reduced IP- ligands require higher potentials for further reduction. Comproportionation constants that describe the equilibrium for the reaction (IP-)(2)AlX + (IP)(2)AlX <-> (IP-)(IP)AlX fall in the range of K-c = 10(5.7) to 10(7.9) for 3-9.