Tj. Boyle et al., Syntheses, characterizations, and X-ray structures of alkali metal derivatives of titanium(IV) neopentoxides, INORG CHEM, 38(10), 1999, pp. 2422-2428
Reactions of titanium(IV) neopentoxide, [Ti(mu-Oneo-Pe)(Oneo-Pe)(3)](2) (1,
Oneo-Pe = OCH2CMe3), with alkali neopentoxides (AOneo-Pe) resulted in the
isolation of the dimeric complexes [ATi(Oneo-Pe)(5)](2) [A = Li (2), Na (3)
, and K (4)], independent of the alkali metal investigated. Each compound w
as characterized by solution and solid-state multinuclear NMR, isopiestic m
olecular weight determination, and/or single-crystal X-ray diffraction. In
the solid state, both 2 and 4 were found to adopt a standard [MM'(OR)(5)](2
) arrangement, wherein the Ti metals are in a distorted trigonal-bipyramida
l geometry and each alkali metal center is four-coordinated. Suitable cryst
als of 3 were not isolated, but solid-state MAS (O-17, C-13, (x)A) NMR spec
troscopy indicated that the solid-state structure of 3 was consistent with
its congeners. Multinuclear (H-1, Li-7, C-13, O-17, Na-23) solution NMR spe
ctroscopy data in toluene revealed that 2 exists in a complex multinuclear
equilibrium, whereas 3 and 4 exist as mononuclear species in solution.