An Air‐ and Water‐Tolerant Zinc Hydride Cluster That Reacts Selectively With CO₂

The reaction of [Zn3Cl3L], in which L(3-) is a tris(β-diketiminate) cyclophane, with K(sBu)3BH afforded [Zn3(μ-H)3L] (2), as confirmed by NMR spectroscopy, NOESY, and X-ray crystallography. The complex 2 was air-stable and unreactive towards water, methanol, and other substrates (e.g., nitriles) at room temperature over 24 h but reacted with CO2 (ca. 1 atm) to generate [Zn3(μ-H)2(μ-1,1-O2CH)] (3). In contrast, [Zn3(OH)3L] (4) was found to be unreactive toward CO2 over the course of several days at 90 °C.