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.

Keywords: Alcohol; Iridium; Ketone; Metal Hydride; Transfer Hydrogenation.