We report the structure, reactivity, and catalytic utility of a triiridium complex, [Ir3H6(µ3-H)(PN)3]2+ (2-H, PN = (2-pyridyl)CH2PBut2). Despite its unusual stability to unsaturated organics, electrophiles, and even CF3SO3D, we find that complex 2-H catalyzes hydrogenation of CO2 to formate (TONIr = 9,600) 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) were 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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