Suppressing Cis/Trans 'Ring-Flipping' in Organoaluminium(III)-2-Pyridyl Dimers-Design Strategies Towards Lewis Acid Catalysts for Alkene Oligomerisation.

Owing to its high natural abundance compared to the commonly used transition (precious) metals, as well as its high Lewis acidity and ability to change oxidation state, aluminium has recently been explored as the basis for a range of single-site catalysts. This paper aims to establish the ground rules for the development of a new type of cationic alkene oligomerisation catalyst containing two Al(III) ions, with the potential to act co-operatively in stereoselective assembly. Five new dimers of the type [R 2 Al(2-py')] 2 (R=Me, i Bu; py'=substituted pyridyl group) with different substituents on the Al atoms and pyridyl rings have been synthesised. The formation of the undesired cis isomers can be suppressed by the presence of substituents on the 6-position of the pyridyl ring due to steric congestion, with DFT calculations showing that the selection of the trans isomer is thermodynamically controlled. Calculations show that demethylation of the dimers [Me 2 Al(2-py')] 2 with Ph 3 C + to the cations [{MeAl(2-py')} 2 (μ-Me)] + is highly favourable and that the desired trans disposition of the 2-pyridyl ring units is influenced by steric effects. Preliminary experimental studies confirm that demethylation of [Me 2 Al(6-MeO-2-py)] 2 can be achieved using [Ph 3 C][B(C 6 F 5 ) 4 ].