Syntheses and structures of cationic and neutral, homo- and heteroleptic tert-butoxides of the group 4 metals.
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(O(t)Bu)(3) reacted with cis-MCl(4)(THF)(2) [M = Zr (1), Hf (2)] in THF solutions to furnish the salts fac-{[M(O(t)Bu)(3)(THF)(3)](SnCl(3))}, which are separated ion pairs featuring weakly coordinating trichlorostannate ions. Neutral complexes, namely, [M(O(t)Bu)(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(O(t)Bu)(3)Cl reacted with silver triflate to give [Ti(O(t)Bu)(2)(OTf)(2)(THF)(2)] (5). Anion exchange of triflate for trichlorostannate transformed 1 to the contact ion pair fac-[Zr(O(t)Bu)(3)OTf(THF)(2)] (6). A total of 2 equiv of NaSn(O(t)Bu)(3) reacted with cis-MCl(4)(THF)(2) to give the complexes fac-[Sn(mu-O(t)Bu)(3)M(O(t)Bu)(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(O(t)Bu)(3)(THF)(3)](SnCl(3))}. 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.
Njua
Edmond Y
EY
Department of Chemistry, University of North Dakota, Grand Forks, North Dakota 58202-9024, USA.
Steiner
Alexander
A
Stahl
Lothar
L