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 δ = −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 °C) and pressures (50 psi of H2). Tuning of the oxorhenium catalysts also resulted in the hydrogenation of tert-butylethylene at room temperature.