Tuning Catalytic Activity in the Hydrogenation of Unactivated Olefins with Transition-Metal Oxos as the Lewis Base Component of Frustrated Lewis Pairs

The steric and electronic demands of the catalytic olefin hydrogenation of tert-butylethylene with oxorhenium/Lewis acid FLPs were evaluated. The sterics of the ligand were altered by installing bulkier isopropyl groups in the 2,6-positions of the diamidopyridine (DAP) ligand. Lewis acid/base adducts were not isolated for complexes with this ligand; however, species incorporating isopropyl groups were still active in catalytic hydrogenation. Modifications were also made to the Lewis acid, and catalytic reactions were performed with Piers' borane, HB(C6F5)(2), and the aluminum analogue Al(C6F5)(3). The rate of catalytic hydrogenation was shown to strongly correlate with the size of the alkyl, aryl, or hydride ligand. This was confirmed by a linear Taft plot with the steric sensitivity factor delta=-0.57, which suggests that reaction rates are faster with sterically larger X substituents. These data were used to develop a catalyst ((MesDAP)Re(O)(Ph)/HB(C6F5)(2)) that achieved a TON of 840 for the hydrogenation of tert-butylethylene at mild temperatures (100 degrees C) and pressures (50 psi of H-2). Tuning of the oxorhenium catalysts also resulted in the hydrogenation of tert-butylethylene at room temperature.