Ligation state of nickel during C-O bond activation with monodentate phosphines.

The oxidative addition of phenolic electrophiles at Ni(0) in the presence of monodentate phosphine ligands was studied with both dispersion-free and dispersion-containing DFT methods. With the popular bulky ligand PCy3, consideration of dispersion has a striking effect on the predicted ligation state of nickel during oxidative addition of aryl sulfamates. Dispersioncontaining methods such as M06L indicate a clear preference for a bis-phosphine ligated transition state (TS), while dispersion free methods like B3LYP strongly favor a monophosphine ligated TS. This discrepancy in predicted ligation state is also found with small phosphines (PMe3) in combination with some aryl electrophiles (carbamates, acetates, pivalates, chlorides), but a bis-PMe3-ligated TS is predicted regardless of dispersion for other electrophiles (sulfamates, mesylates, tosylates). DFT calculations that include dispersion also offer a possible explanation for the observed poor efficacy of P Bu3 as a ligand in Ni-catalyzed cross-coupling reactions.