ja5055687_si_001.cif (4.61 MB)

Lewis Acid Promoted Titanium Alkylidene Formation: Off-Cycle Intermediates Relevant to Olefin Trimerization Catalysis

Download (4.61 MB)
posted on 30.07.2014, 00:00 by Aaron Sattler, David G. VanderVelde, Jay A. Labinger, John E. Bercaw
Two new precatalysts for ethylene and α-olefin trimerization, (FI)­Ti­(CH2SiMe3)2Me and (FI)­Ti­(CH2CMe3)2Me (FI = phenoxy-imine), have been synthesized and structurally characterized by X-ray diffraction. (FI)­Ti­(CH2SiMe3)2Me can be activated with 1 equiv of B­(C6F5)3 at room temperature to give the solvent-separated ion pair [(FI)­Ti­(CH2SiMe3)2]­[MeB­(C6F5)3], which catalytically trimerizes ethylene or 1-pentene to produce 1-hexene or C15 olefins, respectively. The neopentyl analogue (FI)­Ti­(CH2CMe3)2Me is unstable toward activation with B­(C6F5)3 at room temperature, giving no discernible diamagnetic titanium complexes, but at −30 °C the following can be observed by NMR spectroscopy: (i) formation of the bis-neopentyl cation [(FI)­Ti­(CH2CMe3)2]+, (ii) α-elimination of neopentane to give the neopentylidene complex [(FI)­Ti­(CHCMe3)]+, and (iii) subsequent conversion to the imido-olefin complex [(MeOAr2N)­Ti­(OArHCCHCMe3)]+ via an intramolecular metathesis reaction with the imine fragment of the (FI) ligand. If the reaction is carried out at low temperature in the presence of ethylene, catalytic production of 1-hexene is observed, in addition to the titanacyclobutane complex [(FI)­Ti­(CH­(CMe3)­CH2CH2)]+, resulting from addition of ethylene to the neopentylidene [(FI)­Ti­(CHCMe3)]+. None of the complexes observed spectroscopically subsequent to [(FI)­Ti­(CH2CMe3)2]+ is an intermediate or precursor for ethylene trimerization, but notwithstanding these off-cycle pathways, [(FI)­Ti­(CH2CMe3)2]+ is a precatalyst that undergoes rapid initiation to generate a catalyst for trimerizing ethylene or 1-pentene.