Publications

{sup 203,205}Tl NMR Studies of Crystallographically Characterized Thallium Alkoxides. X-Ray Structures of [Tl(OCH{sub 2}CH{sub 3})]4 and [Tl(OAr)]{sub infinity} where OAr = OC{sub 6}H{sub 3}(Me){sub 2}-2,6 and OC{sub 6}H{sub 3}(Pr{sup i}){sub 2}-2,6

Boyle, Timothy J.; Alam, Todd M.; Lang, David P.

[Tl(OCH{sub 2}CH{sub 3})]{sub 4}, (1) was reacted with excess HOR to prepare a series of [Tl(OR)]{sub n} where OR= OCHMe{sub 2} (2, n = 4), OCMe{sub 3} (3, n = 4), OCH{sub 2}CMe{sub 3} (4, n = 4), OC{sub 6}H{sub 3}(Me){sub 2}-2,6 (5, n = {infinity}), and OC{sub 6}H{sub 3}(Pr{sup i}){sub 2}-2,6 (6, n = {infinity}). Single crystal X-ray diffraction was used to determine the structure of compounds ligated by more sterically demanding ligands. Compound 4 was found to adopt a cubane structure, while 5 and 6 formed linear polymeric structures. These compounds were additionally characterized by {sup 203,205}Tl solution and {sup 205}Tl solid state NMR. Compounds 1--4 were found to remain intact in solution while the polymeric species, 5 and 6, appeared to be fluxional. While variations in the solution and solid state structures for the tetrameric [Tl(OR)]{sub 4} and polymeric [Tl(OAr)]{sub {infinity}} may be influenced by the steric hindrance of their respective ligands, the covalency of the species is believed to be more an effect of the parent alcohol acidity.