The various aromatic hydrocarbons (Chart 2) constitute a sharply graded series of sterically encumbered (unhindered, partially hindered, and heavily hindered) donors in electron transfer (ET) to quinones (Chart 1). As such, steric effects provide the quantitative basis to modulate (and differentiate) outer-sphere and inner-sphere pathways provided by matched pairs of hindered and unhindered donors with otherwise identical electron-transfer properties. Thus the hindered donors are characterized by (a) bimolecular rate constants (k(2)) that are temperature dependent and well correlated by Marcus theory, (b) no evidence for the formation of (discrete) encounter complexes, (c) high dependency on solvent polarity, and (d) enhanced sensitivity to kinetic salt effects-all diagnostic of outer-sphere electron-transfer mechanisms. Contrastingly, the analogous unhindered donors are characterized by (a) temperature-independent rate constants (k(2)) that are 10(2) times faster and rather poorly correlated by Marcus theory, (b) weak dependency on solvent polarity, and (c) low sensitivity to kinetic salt effects-all symptomatic of inner-sphere ET mechanisms arising from the preequilibrium formation of encounter complexes with charge-transfer (inner-sphere) character. Steric encumbrances which inhibit strong electronic (charge-transfer) coupling between the benzenoid and quinonoid pi systems are critical for the mechanistic changeover. Thus, the classical outer-sphere/inner-sphere distinction (historically based on coordination complexes) is retained in a modified form to provide at common terminology for inorganic as well as organic (and biochemical) redox systems.