Formation and structures of hafnocene complexes in MAO- and AlBui3/CPh3[B(C6F5)4]-activated systems

Bryliakov, Konstantin P., Talsi, Evgenii P., Voskoboynikov, Alexander Z., Lancaster, Simon J. and Bochmann, Manfred ORCID: https://orcid.org/0000-0001-7736-5428 (2008) Formation and structures of hafnocene complexes in MAO- and AlBui3/CPh3[B(C6F5)4]-activated systems. Organometallics, 27 (23). pp. 6333-6342.

Full text not available from this repository. (Request a copy)

Abstract

The formation of cationic species relevant to olefin polymerization based on (SBI)HfCl2, Me2C(C5H4)(Flu)HfCl2, Ph2C(C5H4)(Flu)HfCl2, and L'HfCl2 activated by MAO, AlMe3/CPh3[B(C6F5)4], and AlBui3/CPh3[B(C6F5)4] (SBI = rac-Me2Si(Ind)2; L' = C2H4(Flu)(5,6-C3H6-2-MeInd)) was studied by 1H, 13C, and 19F NMR spectroscopy. Thermally stable heterobinuclear intermediates of the type [LHf(µ-Me)2AlMe2]+[MeMAO]- and [LHf(µ-Me)2AlMe2]+[B(C6F5)4]- were identified when using MAO and AlMe3/CPh3[B(C6F5)4] as activators, respectively. The stability of these species explains the low productivity of hafnocene catalysts in the presence of AlMe3-containing activators, compared to zirconocenes. By contrast, in the ternary systems LHfCl2/AlBui3/CPh3[B(C6F5)4] hydride species were detected that must be responsible for the formation of the highly active sites in olefin polymerization. The ionic hydrido species differ significantly in stability. The formation of the mixed-alkyl complex L'Hf(Me)CH2SiMe3 proceeds with surprisingly high diastereoselectivity; the sterically more hindered isomer is produced preferentially. It reacts with CPh3[B(C6F5)4] to afford the ion pair [L'Hf-CH2SiMe3]+[B(C6F5)4]- as two diastereomers that exist in dynamic equilibrium. The rates of site epimerization of this ion pair indicate only small energy differences between the two isomers.

Item Type:	Article
Faculty \ School:	Faculty of Science > School of Chemistry (former - to 2024)
UEA Research Groups:	Faculty of Science > Research Groups > Synthetic Chemistry (former - to 2017) Faculty of Science > Research Groups > Chemistry of Light and Energy Faculty of Science > Research Groups > Chemistry of Materials and Catalysis
Depositing User:	Rachel Smith
Date Deposited:	21 Mar 2011 16:22
Last Modified:	24 Sep 2024 09:27
URI:	https://ueaeprints.uea.ac.uk/id/eprint/26776
DOI:	10.1021/om800664p

Actions (login required)

View Item