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Updated: May 24, 2025

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
Published on: November 9, 2019
Reversible CO2 Hydrogenation, Neutron Crystallography, and Hydride Reactivity of a Triiridium Heptahydride Complex
Valeriy Cherepakhin1, Van K Do1, Anthony J Chavez1
1Loker Hydrocarbon Research Institute, Wrigley Institute for Environment and Sustainability, and Department of Chemistry, University of Southern California, Los Angeles, California, 90089-1661, USA.
Abstract:
The authors report the structure, reactivity, and catalytic utility of a triiridium complex, [Ir3H6(μ3-H)(PN)3]2+ (2-H, PN = (2-pyridyl)CH2PBut 2). Despite its unusual stability to unsaturated organics, electrophiles, and even CF3SO3D, they find that complex 2-H catalyzes hydrogenation of CO2 to formate (TONIr = 9600) and reverse formic acid dehydrogenation (TONIr = 54 400). The hydrogenation operates via a reactive intermediate [Ir3H4(μ-H)4(PN)3]+ (5). Neutron crystallography and DFT-supported neutron vibrational spectroscopy of 2-H reveal Ir─H bond lengths and elucidate the vibration modes within the Ir3H7 core. Stoichiometric oxidation of 2-H produces four classes of iridium complexes of varied nuclearity and hydride structure: tetra- and pentanuclear clusters [Ir3H6(μ3-AuPPh3)(PN)3]2+ (2-Au) and [Ag{Ir2H4(μ-OAc)(PN)2}2]3+ (6) are generated using AuPPh3 + and AgOAc, respectively. Further oxidation to class [Ir2H3(μ-X)2(PN)2]+ is possible with AgOAc, Hg(OAc)2, or I2. Finally, a TEMPO/HCl system completely oxidizes the hydrides and gives [Ir2Cl4(μ-Cl)2(PN)2] (11).
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