To further explore the reactivity and redox capability of the bis-arylimino acenaphthylene ligand (BIAN) in early transition metal complexes, the coordinatively unsaturated titanium synthons, [(dpp-BAAN)Ti(R)(2)] ([dpp-BAAN](2-) = N,N'-bis(2,6-diisopropylphenylamido)acenaphthylene and R = (OBu)-Bu-t (2) or CH2C(CH3)(3) (3)), in which the BAAN ligand is reduced by two electrons, were isolated in good yields via sterically induced radical elimination reactions. Addition of p-tolyl azide to complex 3 initiated reductive elimination of the neopentyl ligands to generate a putative imido species. The imido species was trapped by a second oxidative addition of chloride ligands to yield the titanium imido complex, [(dpp-BIAN)Ti[=N(4-C6H4Me)]Cl-2 (4). These reactions demonstrate that the BAAN ligand can provide redox equivalents for enhanced reactivity that includes oxidative addition and reductive elimination at d(0) metal centers.