New sterically encumbered tripodal aminetris(aryloxide) ligands N(CH₂C₆H₂-3-^tBu-5-X-2-OH)₃ (^tBu,XLH₃) with relatively electron-rich phenols are prepared by Mannich condensation (X = OCH₃) or by a reductive amination/Hartwig−Buchwald amination sequence on the benzyl-protected bromosalicylaldehyde (X = N[C₆H₄-p-OCH₃]₂), followed by debenzylation using Pearlman’s catalyst (Pd(OH)₂/C). The analogous dianisylamino-substituted compound lacking the tert-butyl group ortho to the phenol (^H,An₂NLH₃) is also readily prepared. The ligands are metalated by titanium(IV) tert-butoxide to form the five-coordinate alkoxides LTi(O^tBu). Treatment of the tert-butoxides with aqueous HCl yields the five-coordinate chlorides LTiCl, and with acetylacetone gives the six-coordinate diketonates LTi(acac). The diketonate complexes ^tBu,XLTi(acac) show reversible ligand-based oxidations with first oxidation potentials of +0.57, +0.33, and −0.09 V (vs ferrocene/ferrocenium) for X = ^tBu, MeO, and An₂N, respectively. Both dianisylamine-substituted complexes ^R,An₂NLTi(acac) (R = ^tBu, H) show similar electrochemistry, with three one-electron oxidations closely spaced at ∼0 V and three oxidations due to removal of a second electron from each diarylaminoaryloxide arm at ∼ + 0.75 V. The new electron-rich tripodal ligands therefore have the capacity to release multiple electrons at unusually low potentials for aryloxide groups.