The utility of tri-tert-butoxystannate as a chelating tridentate ligand for group 4 metals was investigated. The highly Lewis acidic metals degraded the stannate ion in a series of tert-butoxide abstraction steps to produce a variety of group 4 tert-butoxides. A total of 1 equiv of NaSn((OBu)-Bu-t)(3) reacted with cis-MCl4(THF)(2) [M = Zr (1), Hf (2)] in THF solutions to furnish the salts fac-{[M((OBu)-Bu-t)(3)(THF)(3)](SnCl3)}, which are separated ion pairs featuring weakly coordinating trichlorostannate ions. Neutral complexes, namely, [M((OBu)-Bu-t)(2)Cl-2(THF)(2)] [M = Zr (3), Hf (4)], were isolated when (2)/(3) equiv of sodium stannate was used in these reactions. Titanium tetrachloride formed analogues neither of 1 and 2 nor of 3 and 4, but Ti((OBu)-Bu-t)(3)Cl reacted with silver triflate to give [Ti((OBu)-Bu-t)(2)(OTf)(2)(THF)(2)] (5). Anion exchange of triflate for trichlorostannate transformed 1 to the contact ion pair fac-[Zr((OBu)-Bu-t)(3)OTf(THF)(2)] (6). A total of 2 equiv of NaSn((OBu)-Bu-t)(3) reacted with cis-MCl4(THF)(2) to give the complexes fac-[Sn(mu-(OBu)-Bu-t)(3)M((OBu)-Bu-t)(3)] [M = Zr (7), Hf (8)]. Tri-tert-butoxystannate may be used as a selective alkoxylating agent for group 4 metals, and it can be transferred to these metals intact if their Lewis acidity is appropriately attenuated as in fac-{[M((OBu)-Bu-t)(3)(THF)(3)](SnCl3)}. Single-crystal X-ray studies revealed distorted octahedral coordination geometries for all compounds (1-8), with 1, 2, 7, and 8 being crystallographically C-3 symmetric.