Center for Catalysis, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA).
Department of Chemistry, University of Florida, Gainesville, FL 32611-7200 (USA).
Angew Chem Int Ed Engl. 2015 Jun 8;54(24):7047-50. doi: 10.1002/anie.201501539. Epub 2015 Apr 27.
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.
化合物 [Zn3Cl3L](其中 L(3-) 为三(β-二酮亚胺)环戊二烯)与 K(sBu)3BH 反应得到 [Zn3(μ-H)3L](2),这一点通过 NMR 光谱、NOESY 和 X 射线晶体学得到了证实。室温下,配合物 2 在 24 小时内对空气稳定,且不与水、甲醇和其他底物(如腈)反应,但与 CO2(约 1atm)反应生成 [Zn3(μ-H)2(μ-1,1-O2CH)](3)。相比之下,在 90°C 下几天的时间内,[Zn3(OH)3L](4)对 CO2 表现出不反应性。