Rational Design of a Catalyst for the Selective Monoborylation of Methane

Combined computational and experimental studies elucidate the mechanism and suggest rational design and optimization strategies of a bis­(phosphine)-supported iridium-catalyst for methane monoborylation. The activation of the C–H bond in methane via oxidative addition using tris­(boryl) iridium­(III) complexes bearing bis-chelating supporting ligands is modeled computationally. This model shows that the use of the soft Lewis base ligand such as 1,2-bis­(dimethylphosphino)­ethane (dmpe) lowers the activation barrier of the rate-determining step as it facilitates polarization of the metal-center, lowering the barrier of the oxidative addition to afford a seven-coordinate iridium­(V) intermediate. The experimental optimization of this reaction using high-throughput methods shows that up to 170 turnovers can be achieved at 150 °C (500 psi) within 16 h using bis­(pinacolato)­diboron, a well-defined homogeneous and monomeric catalyst (dmpe)­Ir­(COD)Cl that is readily available from commercial precursors, with selectivity for the monoborylation product. High-boiling cyclic aliphatic solvents decalin and cyclooctane also prove suitable for this reaction, while being inert toward borylation. In accordance with the lower calculated activation barrier, catalytic turnover is also observed at 120 °C with up to 50 turnovers over the course of 4 days in cyclohexane solvent. It was found that the borylation of methane is only achieved via one catalytic cycle, and buildup of pinacolborane, a side-product from methane borylation with bis­(pinacolato)­diboron, inhibits catalytic activity.