A study of representative alcohol, alkoxide, thiol and thiolate complexes of B(C 6F 5) 3; their roles as activators of zirconocene olefin polymerization initiators

• Published in: Inorganica Chimica Acta 2002-06, Vol.335, p.43-51
• Main Authors: Drewitt, Mark J., Niedermann, Martina, Kumar, Rajesh, Baird, Michael C.
• Format: Article
• Language: English
• Subjects: Alkoxide complexes; Borate complexes; Olefin polymerization; Thiolate complexes
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/S0020-1693(02)00836-8

The highly electrophilic borane B(C 6F 5) 3 reacts with n-octadecanol ( n-C 18H 37OH) and n-octadecanethiol ( n-C 18H 37SH) to form equilibrium mixtures of reactants and the 1:1 adducts ( n-C 18H 37EH)B(C 6F 5) 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 [C 10H 6(NMe 2) 2H][( n-C 18H 37O)B(C 6F 5) 3] and [C 10H 6(NMe 2) 2H][( n-C 18H 37S)B(C 6F 5) 3], respectively, and by Cp 2ZrMe 2 to give methane and, apparently, the unstable zirconium complexes [Cp 2ZrMe][( n-C 18H 37E)B(C 6F 5) 3]. The alcohol, alkoxide, thiol and thiolate systems are characterized in solution by 1H, 19F, 13C{ 1H} and 11B 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(C 6F 5) 3. The highly electrophilic borane B(C 6F 5) 3 reacts with n-octadecanol ( n-C 18H 37OH) and n-octadecanethiol ( n-C 18H 37SH) to form equilibrium mixtures of reactants and the 1:1 adducts ( n-C 18H 37EH)B(C 6F 5) 3 (E=O, S); equilibrium constants for these reactions are determined. The adducts are deprotonated by 1,8-bis (dimethylamino) naphthalene to form the salts [C 10H 6(NMe 2) 2H][( n-C 18H 37E)B(C 6F 5) 3], and by Cp 2ZrMe 2 to give methane and, apparently, the unstable zirconium complexes [Cp 2ZrMe][( n-C 18H 37E)B(C 6F 5) 3]. It is also shown that proton sponge can coordinate in monodentate fashion to B(C 6F 5) 3.