A redox-active, tetradentate ligand, N,N'-bis-(3-dimethylamino-propyl)-4,5-dimethoq-benzene-1,2-diamide ([N2N2cat](2-)), was developed, and the six-coordinate metal complexes [N2N2cat]TiCl2 (3) and [N2N2cat]ZrCl2 (4) were synthesized. The tetradentate ligand was determined to be fluxional in 3 and 4, enabled by reversible dissociation of the neutral amine groups of the [N2N2cat](2-) ligand. Both amine arms of 3 could be replaced by N,N-dimethylaminopyridine with an overall free energy change of -4.64(3) kcal mol(-1) at 298 K. Cyclic voltammetry experiments were used to probe the redox capabilities of the [N2N2cat](2-) ligand: complex 3 exhibited two one-electron oxidations at -0.19 and -0.52 V versus [Cp2Fe](+/0) while 4 exhibited a single two-electron oxidation at 0.55 V. Substitution of the chlorides in 3 for an imide afforded the dimer {[N2N2cat]Ti(mu-p-NC6H4Me)}(2), in which the metal centers are five-coordinate because of dissociation of one amine arm of the [N2N2cat](2-) ligand. While the bis-azide complex [N2N2cat]Ti(N-3)(2) was stable toward elimination of N-2, the bis-phenylacetylide complex [N2N2cat]Ti(C CPh)(2) could be oxidized by PhICl2, resulting in subsequent reductive elimination of 1,4-diphenybutadiyne.