A New Mechanism of Metal-Ligand Cooperative Catalysis in Transfer Hydrogenation of Ketones.

ABSTRACT

We report iridium catalysts IrCl(η5-Cp*)(κ2-(2-pyridyl)CH2NSO2C6H4X) (1-Me, X = CH3 and 1-F, X = F) for transfer hydrogenation of ketones with 2-propanol that operate by a previously unseen metal-ligand cooperative mechanism. Under the reaction conditions, complexes 1 (1-Me and 1-F) derivatize to a series of catalytic intermediates Ir(η5-Cp*)(κ2-(C5H4N)CHNSO2Ar) (2), IrH(η5Cp*)(κ2-(2-pyridyl)CH2NSO2Ar) (3), and Ir(η5-Cp*)(κ3-(2-pyridyl)CH2NSO2Ar) (4). The structures of 1-Me and 4-Me were established by single-crystal X-ray diffraction. A rate-determining, concerted hydrogen transfer step (2 + R2CHOH ⇄ 3 + R2CO) is suggested by kinetic isotope effects, Eyring parameters (ΔH ≠ = 29.1(8) kcal mol-1 and ΔS ≠ = -17(19) eu), proton-hydride fidelity, and DFT calculations. According to DFT, a nine-membered cyclic transition state is stabilized by an alcohol molecule that serves as a proton shuttle.