Fluorinated bismuth alkoxides: from monomers to polymers and oxo-clusters

A series of new bismuth fluoroalkoxide compounds have been prepared through the treatment of 1,1,1,3,3,3-hexa fluoro-2-propanol with BiAr(3) (where Ar = Ph, p-Tol). Reactions were conducted without the use of any additional solvent and the reaction products distilled or extracted with non-polar or polar Lewis base solvents. Structural analyses reveal that under variable reaction conditions the interaction of BiAr(3) with (CF(3))(2)CHOH can give a mixture of bismuth complexes with varying degrees of substitution, cluster formation and aggregation. Compounds [Bi(OCH(CF(3))(2))(3)(pyr)(2)] (2) (pyr = pyridine), [Bi(OCH(CF(3))(2))(3)(thf)(3)] (3) (thf = tetrahydrofuran), [Bi(2)(OCH(CF(3))(2))(3)(dabco)(3)] (4) (dabco = 1,4-diazabicyclo[2.2.2]octane), [PhBi(OCH(CF(3))(2))(2)](n) (5), [Bi(2)O(OCH(CF(3))(2))(4)(C(7)H(8))](2) (6) (C(7)H(8) = toluene), [Bi(9)O(7)(OCH(CF(3))(2))(13)] (7), [Bi(2)O(OCH(CF(3))(2)) 4(Et(2)O)](2) (8), [Bi(2)O(OCH(CF(3))(2))(4)(thf)](2) (9) and [Bi(2)O(OCH(CF(3))(2))(4)(tmeda)(2)] (10) (tmeda = N, N, N', N'-tetramethylethylenediamine) have been fully characterised including by single crystal X-ray diffraction.