© 2015 American Chemical Society. Ferrocenyl phosphine thioether ligands (PS), not containing deprotonatable functions, efficiently support the iridium catalyzed ketone hydrogenation in combination with a strong base cocatalyst. Use of an internal base ([Ir(OMe)(COD)] 2 in place of [IrCl(COD)] 2 ) is not sufficient to ensure activity and a strong base is still necessary, suggesting that the active catalyst is an anionic hydride complex. Computational investigations that include solvent effects demonstrate the thermodynamically accessible generation of the tetrahydrido complex [IrH 4 (PS)] - and suggest an operating cycle via a [Na + (MeOH) 3 ⋯Ir - H 4 (PS)] contact ion pair with an energy span of 18.2 kcal/mol. The cycle involves an outer sphere stepwise H - /H + transfer, the proton originating from H 2 after coordination and heterolytic activation. The base plays the dual role of generating the anionic complex and providing the Lewis acid cocatalyst for ketone activation. The best cycle for the neutral system, on the other hand, requires an energy span of 26.3 kcal/mol. This work highlights, for the first time, the possibility of outer sphere hydrogenation in the presence of non deprotonatable ligands and the role of the strong base in the activation of catalytic systems with such type of ligands.
- bifunctional ligands
- catalyzed transfer hydrogenation
- DFT calculations
- effect of strong base