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Water adds to the two-electron mixed-valence Ir0,II2 core of Ir2(tfepma)3Cl2 (tfepma = MeN[P(OCH2CF3)2]2) to cleanly generate an IrI,III2 hydride. Dehydrohalogenation across the Ir–Ir bond returns the complex to an Ir0,II2 species.

Graphical abstract: Water addition to a two-electron mixed-valence bimetallic center

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