Nature Chemistry

Computational study of the mechanism of formation and C-H borylation

We have used f-in-core relativistic effective core potentials^29,30 to build a thermodynamic picture of the mechanism, considering both electron and ligand transfer^31-33, and many steps. The pathway in Fig. 5 was found most favourable for large X ligands (for smaller X see route B, Fig. SI.31). The first step shows concerted benzene binding and X transfer between two UX₃ fragments and benzene, forming UX₂(benzene) and UX₄, II. A second concerted coordination/X transfer process then takes place, where one UX₃ fragment associates to the benzene unit of UX₂(benzene) as a second UX₃ accepts a ligand from it, giving the final products, III.