Isolation and crystal structure of a water-soluble iridium hydride: A robust and highly active catalyst for acid-catalyzed transfer hydrogenations of carbonyl compounds in acidic media

This paper reports the isolation and structural determination of a water-soluble hydride complex [Cp*Ir^III(bpy)H]⁺ (1, Cp* = η⁵-C₅Me₅, bpy = 2,2′-bipyridine) that serves as a robust and highly active catalyst for acid-catalyzed transfer hydrogenations of carbonyl compounds at pH 2.0-3.0 at 70 °C. The catalyst 1 was synthesized from the reaction of a precatalyst [Cp*Ir^III(bpy)(OH₂)₂]²⁺ (2) with hydrogen donors HCOOX (X = H or Na) in H₂O under controlled conditions (2.0 < pH < 6.0, 25 °C) which avoid protonation of the hydrido ligand of 1 below pH ca. 1.0 and deprotonation of the aqua ligand of 2 above pH ca. 6.0 (pK_a value of 2 = 6.6). X-ray analysis shows that complex 1 adopts a distorted octahedral geometry with the Ir atom coordinated by one η⁵-Cp*, one bidentate bpy, and one terminal hydrido ligand that occupies a bond position. The isolation of 1 allowed us to investigate the robust ability of 1 in acidic media and reducing ability of 1 in the reaction with carbonyl compounds under both stoichiometric and catalytic conditions. The rate of the acid-catalyzed transfer hydrogenation is drastically dependent on pH of the solution, reaction temperature, and concentration of HCOOH. The effect of pH on the rate of the transfer hydrogenation is rationalized by the pH-dependent formation of 1 and activation process of the carbonyl compounds by protons. High turnover frequencies of the acid-catalyzed transfer hydrogenations at pH 2.0-3.0 are ascribed not only to nucleophilicity of 1 toward the carbonyl groups activated by protons but also to a protonic character of the hydrido ligand of 1 that inhibits the protonation of the hydrido ligand.