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

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.

Iridium-based hydride transfer catalysts: from hydrogen storage to fine chemicals.

Selective hydrogen transfer remains a central research focus in catalysis: hydrogenation and dehydrogenation have central roles, both historical and contemporary, in all aspects of fuel, agricultural, pharmaceutical, and fine chemical synthesis. Our lab has been involved in this area by designing homogeneous catalysts for dehydrogenation and hydrogen transfer that fill needs ranging from on-demand hydrogen storage to fine chemical synthesis. A keen eye toward mechanism has enabled us to develop systems with excellent selectivity and longevity and demonstrate these in a diversity of high-value applications. Here we describe recent work from our lab in these areas that are linked by a central mechanistic trichotomy of catalyst initiation pathways that lead highly analogous precursors to a diversity of useful applications.

Conformational twisting of a formate-bridged diiridium complex enables catalytic formic acid dehydrogenation.

We previously reported that iridium complex 1a enables the first homogeneous catalytic dehydrogenation of neat formic acid and enjoys unusual stability through millions of turnovers. Binuclear iridium hydride species 5a, which features a provocative C2-symmetric geometry, was isolated from the reaction as a catalyst resting state. By synthesizing and carefully examining the catalytic initiation of a series of analogues to 1a, we establish here a strong correlation between the formation of C2-twisted iridium dimers analogous to 5a and the reactivity of formic acid dehydrogenation: an efficient C2 twist appears unique to 1a and essential to catalytic reactivity.