A study of representative alcohol, alkoxide, thiol and thiolate complexes of B(C6F5)3; their roles as activators of zirconocene olefin polymerization initiators

The highly electrophilic borane B(C6F5)(3) reacts with n-octadecanol (n-C18H37OH) and n-octadecanethiol (n-C18H37SH) to form equilibrium mixtures of reactants and the 1:1 adducts (n-C18H37EH)B(C6F5)(3) (E=O, S); equilibrium constants for adduct formation are determined. The adducts are deprotonated by 1,8-bis(dimethylamino)naphthalene (proton sponge) to form the salts [C10H6(NMe2)(2)H][(n-C18H37O)B(C6F5)(3)] and [C10H6(NMe2)(2)H][(n-C18H37S)B(C6F5)(3)], respectively, and by Cp2ZrMe2 to give methane and, apparently, the unstable zirconium complexes [Cp2ZrMe][(n-C18H37E)B(C6F5)(3)]. The alcohol, alkoxide, thiol and thiolate systems are characterized in solution by H-1, F-19, C-13{H-1} and B-11 NMR spectroscopy and in the solid state by FAB mass spectrometry, and it is also shown that proton sponge can coordinate in monodentate fashion to B(C6F5)(3). (C) 2002 Published by Elsevier Science B.V.