An Air‐ and Water‐Tolerant Zinc Hydride Cluster That Reacts Selectively With CO 2

The reaction of [Zn 3 Cl 3 L ], in which L 3− is a tris(β‐diketiminate) cyclophane, with K( s Bu) 3 BH afforded [Zn 3 (μ‐H) 3 L ] ( 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 CO 2 (ca. 1 atm) to generate [Zn 3 (μ‐H) 2 (μ‐1,1‐O 2 CH)] ( 3 ). In contrast, [Zn 3 (OH) 3 L ] ( 4 ) was found to be unreactive toward CO 2 over the course of several days at 90 °C.